Overlapping methods

Abstract

A method for the ring-opening copolymerization of epoxides with carbon dioxide to prepare polycarbonates is described. Catalysts useful in the above method are also described. Heterobimetallic catalysts offer several advantages over catalysts traditionally used in this method. According to a first aspect of the present invention, there is provided a method for preparing polycarbonates, the method comprising: a) contacting carbon dioxide with at least one epoxide, wherein step a) is carried out in the presence of a compound of formula I, as defined herein.

Description

[Technical Field]

[0001] Introduction The present invention relates to a polymerization process for preparing polycarbonates in the presence of a catalyst compound. More particularly, the present invention relates to the ring-opening copolymerization of an epoxide with carbon dioxide to prepare polycarbonates, the ring-opening copolymerization being carried out in the presence of a catalyst compound. The present invention also relates to the catalyst compound itself. [Background technology]

[0002] Background of the Invention The preparation of polycarbonates by ring-opening copolymerization (ROCOP) of epoxides in the presence of CO2 appears to be an attractive means of utilizing CO2, a particularly undesirable greenhouse gas. Polycarbonates formed from ROCOP of epoxides have been touted as an alternative starting point in polyurethane synthesis, with applications as flexible and rigid foams, elastomers, coatings, adhesives, and scratch-resistant materials. 1,2,3,4,5,6 The synthesis of polyurethanes using polycarbonates formed from epoxide ROCOPs shows reduced greenhouse gas emissions and fossil fuel consumption in a life cycle analysis compared to polyurethane production starting with polyether polyols.

[0003] The coupling reaction of CO with epoxides such as propylene oxide (PO) has two competing reaction pathways: the first, copolymerization reaction to form polypropylene carbonate (PPC), and the second, cyclization reaction to form propylene carbonate (PC), which is the thermodynamic product of these two competing reactions. Highly optimized catalysts and conditions are required to disable the cyclization reaction and thus promote the copolymerization to form PPC.

[0004] Several CO2 / epoxide ring-opening monometallic catalysts have been previously reported, with a significant focus on transition metal salen derivatives of Co(III), Cr(III), and Al(III). 7,8,9,10,11 However, these catalysts typically only work well in combination with an external cocatalyst, such as bis(triphenylphosphine)iminium chloride (PPNCl), to form a binary catalyst system, where the cocatalyst is required to improve rate and selectivity. However, the use of such cocatalysts is generally undesirable due to their high cost, toxicity, insolubility, corrosiveness to steel, complex mechanistic rate laws, and loss of activity upon dilution of the binary catalyst formulation. Furthermore, as bimolecular processes, such systems are optimized at high catalyst loadings and high concentration conditions, which impose a cap on the molecular weight of the formed polymer. Furthermore, these binary systems typically produce cyclic carbonate by-products at high temperatures, thereby limiting their potential applications. 12,13,14,15 .

[0005] A common strategy to overcome the many limitations of bimetallic catalyst systems is to tether a cocatalyst to a salen motif. Lee et al. reported a Co(III) salen complex para-functionalized with ammonium 2,4-dinitrophenolate ions, which showed higher turnover frequencies at lower catalyst loadings compared to monometallic catalysts. 16,17 However, such salen ligands with side-chain cocatalysts are often very difficult to synthesize and can only be isolated after complex workup and purification procedures. Furthermore, the use of salen ligands with side-chain cocatalysts in the synthesis of polyols, which are precursors to polyurethanes, often requires undesirable levels of acidity in the reaction conditions to control the molar mass and end-group chemistry.

[0006] Therefore, there remains a need for catalysts for the ROCOP of epoxides in the presence of CO. The present invention was devised with the above in mind. [Prior art documents] [Chartered documents]

[0007] [Non-licensed document 1] AM Chapman, C. Keyworth, MR Kember, AJJ Lennox, CK Williams, ACS Catal. 2015, 5, 1581-1588. [Non-licensed document 2] N. von der Assen, A. Bardow, Green Chem. 2014, 16, 3272-3280. [Non-licensed document 3] SH Lee, A. Cyriac, JY Jeon, BY Lee, Polym. Chem. 2012, 3, 1215.

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[0008] Summary of the Invention According to a first aspect of the present invention, there is provided a method for preparing a polycarbonate, the method comprising: a) contacting carbon dioxide with at least one epoxide Including, A method is provided wherein step a) is carried out in the presence of a compound of formula I as defined herein.

[0009] According to a second aspect of the present invention, there is provided a method for preparing a polyester, the method comprising: a) contacting at least one epoxide with at least one cyclic anhydride Including, A method is provided wherein step a) is carried out in the presence of a compound of formula I as defined herein.

[0010] According to a third aspect of the present invention, there is provided a compound having a structure according to Formula I, as defined herein. Optionally preferred and preferred features of the first aspect of the invention are, to the extent that they share common features, optional and preferred features of the second and third aspects of the invention respectively. The present invention provides, for example, the following items. (Item 1) 1. A method for preparing a polycarbonate, said method comprising: a) contacting carbon dioxide with at least one epoxide Including, Step a) is the reaction of a compound of formula I shown below:

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[0011] [Figure 1] Figure 1 shows an Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of the molecular structure of complex 1. For clarity, disorder and hydrogen atoms have been omitted, and the thermal ellipsoid is shown at 50% probability. [Figure 2] Figure 2 shows an ORTEP diagram of the molecular structure of complex 2, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. [Figure 3] Figure 3 shows ORTEP diagrams of the molecular structures of complex 7 (top) and complex 7-(EtOH) (bottom), with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. [Figure 4] Figure 4 shows an ORTEP diagram of the molecular structure of complex 12, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Two molecules of complex 12 are shown coordinated to each other via acetate co-ligands. [Figure 5] FIG. 5 shows an ORTEP diagram of the molecular structure of complex 10, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. [Figure 6] Figure 6 shows the polymerization data for complex 2: a) PPC molar mass (Mn: ■) and dispersity (

number

[0012] Detailed Description of the Invention definition The term "(m-nC)" or "(m-nC) group" used alone or as a prefix, refers to any group having m to n carbon atoms.

[0013] The term "alkyl," as used herein, refers to a straight- or branched-chain alkyl moiety typically having 1, 2, 3, 4, 5, or 6 carbon atoms. This term includes reference to groups such as methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n-butyl, sec-butyl, or tert-butyl), pentyl, hexyl, etc. Optimally, an alkyl can have 1, 2, 3, or 4 carbon atoms.

[0014] The term "alkylene," as used herein, refers to the divalent equivalent of an alkyl group as defined above.

[0015] The term "alkenyl," as used herein, refers to a straight- or branched-chain alkenyl moiety typically having 1, 2, 3, 4, 5, or 6 carbon atoms. This term includes reference to alkenyl moieties containing 1, 2, or 3 carbon-carbon double bonds (C=C). This term includes reference to groups such as ethenyl (vinyl), propenyl (allyl), butenyl, pentenyl, and hexenyl, and both cis- and trans-isomers thereof.

[0016] The term "alkenylene," as used herein, refers to the divalent equivalent of an alkenyl group as defined above.

[0017] The term "alkynyl," as used herein, refers to a straight- or branched-chain alkynyl moiety typically having 1, 2, 3, 4, 5, or 6 carbon atoms. This term includes reference to alkynyl moieties containing 1, 2, or 3 carbon-carbon triple bonds (C≡C). This term includes reference to groups such as ethynyl, propynyl, butynyl, pentynyl, and hexynyl.

[0018] The term "alkynylene," as used herein, refers to the divalent equivalent of an alkynyl group described above.

[0019] The term "heteroaliphatic," as used herein, refers to a straight-chain or branched alkyl, alkenyl, or alkynyl group, as defined herein, in which one or more (e.g., up to five, preferably up to three, more preferably up to one) carbon atoms are replaced by a heteroatom selected from N, O, and S, provided that the number of carbon atoms is greater than or equal to the number of heteroatoms.

[0020] The term "haloalkyl," as used herein, refers to an alkyl group substituted with one or more halogens (e.g., F, Cl, Br, or I). This term includes reference to groups such as 2-fluoropropyl, 3-chloropentyl, and perfluoroalkyl groups such as perfluoromethyl.

[0021] The term "alkoxy" as used herein refers to -O-alkyl, where alkyl is straight or branched and contains 1, 2, 3, 4, 5, or 6 carbon atoms. In one class of embodiments, alkoxy has 1, 2, 3, or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy, and the like.

[0022] The term "aryl" or "aromatic," as used herein, refers to an aromatic ring system containing 6, 7, 8, 9, or 10 ring carbon atoms. Aryl is often phenyl, but may be a polycyclic ring system having two or more rings, at least one of which is aromatic. The term includes reference to groups such as phenyl, naphthyl, etc.

[0023] The term "aryl(m-nC)alkyl" means an aryl group covalently linked to a (m-nC)alkylene group, both of which are described herein. Examples of aryl-(m-nC)alkyl groups include benzyl, phenylethyl, and the like.

[0024] The term "heteroaryl" or "heteroaromatic" refers to a monocyclic, bicyclic, or polycyclic aromatic ring incorporating one or more (e.g., 1 to 4, particularly 1, 2, or 3) heteroatoms selected from nitrogen, oxygen, or sulfur. Examples of heteroaryl groups are monocyclic and bicyclic groups containing 5 to 12 ring members, and more usually 5 to 10 ring members. A heteroaryl group can be, for example, a 5- or 6-membered monocyclic ring, or a 9- or 10-membered bicyclic ring, e.g., a 5- and 6-membered fused ring, or a bicyclic structure formed from two 6-membered fused rings. Each ring can contain up to about four heteroatoms, typically selected from nitrogen, sulfur, and oxygen. Typically, a heteroaryl ring contains up to three heteroatoms, more usually up to two, e.g., a single heteroatom.

[0025] The term "heteroaryl(m-nC)alkyl" means a heteroaryl group covalently linked to a (m-nC)alkylene group, both of which are described herein.

[0026] The terms "carbocyclyl," "carbocyclic," or "carbocycle" refer to a non-aromatic, saturated or partially saturated monocyclic ring system, or a fused, bridged, or spiro bicyclic carbocyclic ring system. Monocyclic carbocyclic rings contain about 3 to 12 (preferably 3 to 7) ring atoms. Bicyclic carbocyclic rings contain 7 to 17 carbon atoms in the ring, preferably 7 to 12 carbon atoms in the ring. Bicyclic carbocyclic rings may be fused, spiro, or bridged ring systems.

[0027] The terms "heterocyclyl," "heterocyclic," or "heterocycle" refer to a non-aromatic, saturated or partially saturated monocyclic ring system, fused, bridged, or spiro bicyclic heterocyclic ring system. Monocyclic heterocyclic rings contain about 3 to 12 (preferably 3 to 7) ring atoms, including 1 to 5 (preferably 1, 2, or 3) heteroatoms selected from nitrogen, oxygen, or sulfur in the ring. Bicyclic heterocyclic rings contain 7 to 17 member atoms, preferably 7 to 12 member atoms in the ring. Bicyclic heterocyclic rings may be fused, spiro, or bridged ring systems.

[0028] The term "halogen" or "halo," as used herein, refers to F, Cl, Br, or I. In particular, a halogen may be F or Cl, of which Cl is more common.

[0029] The term "epoxide," as used herein, refers to any compound containing an epoxide moiety. An epoxide substrate may contain more than one epoxide moiety, i.e., a bis-epoxide, tris-epoxide, or multi-epoxide-containing moiety. It is understood that reactions carried out in the presence of one or more compounds having more than one epoxide moiety may result in crosslinking of the resulting polymer. It is understood that the term "epoxide" is intended to encompass one or more epoxides. In other words, the term "epoxide" refers to a single epoxide or a mixture of two or more different epoxides.

[0030] The term "substituted" when used herein in reference to a moiety means one or more, particularly up to five. Preferably, "substituted" when used herein in reference to a moiety means that one, two, or three hydrogen atoms in the moiety are independently replaced with the corresponding number of substituents described. Even more preferably, "substituted" when used herein in reference to a moiety means that one or two hydrogen atoms in the moiety are independently replaced with the corresponding number of substituents described. The term "optionally substituted" when used herein means substituted or unsubstituted.

[0031] It will, of course, be understood that substituents are present only at chemically possible locations where one skilled in the art can determine (either experimentally or theoretically) without undue effort whether a particular substitution is possible. Catalytic process for preparing polycarbonates

[0032] According to a first aspect of the present invention, there is provided a method for preparing a polycarbonate, the method comprising: a) contacting carbon dioxide with at least one epoxide Including, Step a) is the reaction of a compound of formula I shown below: [ka] (In the formula, M 1 is selected from the group consisting of Group 2 metals, Group 3 metals, transition metals, Group 13 metals, Group 14 metals and lanthanides; M 2 is selected from Group 1 metals, Group 2 metals, Group 3 metals, Group 13 metals and lanthanides; R 1 is selected from (2-5C) alkylene, (2-5C) alkenylene and (2-5C) alkynylene, wherein 0, 1 or 2 carbon atoms in any one of said (2-5C) alkylene, (2-5C) alkenylene and (2-5C) alkynylene are replaced by a heteroatom selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene, (2-5C) alkenylene and (2-5C) alkynylene are replaced by one or more R x and optionally substituted independently by R x are halo, hydroxy, cyano, nitro, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) haloalkyl, (1-20C) alkoxy, aryl, heteroaryl, and -NR xa R xb are independently selected from R x Any of the aryl or heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-20C)alkyl, (1-20C)haloalkyl, and (1-20C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or Two or more R's located on adjacent atoms xare linked to each other so that, when taken together with the atoms to which they are attached, they form a monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-20C)alkyl, (1-20C)haloalkyl, and (1-20C)alkoxy; R 2 are each absent, hydrogen, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 2a , -C(O)-OR 2a and -C(O)-NR 2a R 2b are independently selected from R 2 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl; X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4 are each independently selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl; R 4wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl and heteroaryl(1-2C)alkyl are optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy; E 1 is C and E 2 is O, S or N, or E 1 is N and E 2 is O, R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 3a , -C(O)-OR 3a , -OC(O)-R 3a , -C(O)-NR 3a R 3b , -N(R 3a )C(O)-R 3b and -NR 3a R 3b are independently selected from R 3 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; and / or Two Rs located on adjacent atoms 3are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system, any of said monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; each n is independently selected from 0, 1, 2, and 3; L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) heteroaliphatic, carbocyclyl, carbocyclyl(1-3C) alkyl, heterocyclyl, heterocyclyl(1-3C) alkyl, aryl, aryl(1-3C) alkyl, heteroaryl, heteroaryl(1-3C) alkyl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) ywhere x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2 Any of the (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, and heteroaryl(1-3C)alkyl groups may contain one or more R b where L is optionally substituted by 1 and L 2 provided that at least one of R a is independently selected from hydrogen, (1-25C)alkyl, (2-25C)alkenyl, (2-25C)alkynyl, (1-25C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, and heteroaryl(1-3C)alkyl; R a any (1-25C)alkyl, (2-25C)alkenyl, (2-25C)alkynyl, (1-25C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, or heteroaryl(1-3C)alkyl occurring therein is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; R b are each independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; G1 and G 2 is independently selected from absent and a neutral or anionic donor ligand that is a Lewis base; Q is a compound according to the structure QI or Q-II shown below: [ka] and X 2 are each independently absent or (1-3C)alkylene, said (1-3C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; X 3 are each independently absent or (1-3C)alkylene, said (1-3C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; X 4 each independently is absent or methylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; m is 1, 2, 3 or 4; R 5 are respectively hydrogen, halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 5a , -C(O)-OR 5a , -OC(O)-R 5a , -C(O)-NR 5a R 5b , -N(R 5a )C(O)-R 5b and -NR 5a R 5b are independently selected from R 5wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-3C) alkyl; and / or Two Rs located on adjacent atoms 5 are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system, any of said monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; R 6 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 6a , -C(O)-OR 6a , -OC(O)-R 6a , -C(O)-NR 6a R 6b , -N(R 6a )C(O)-R 6b and -NR 6a R 6b are independently selected from R 6 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 6aand R 6b are independently selected from hydrogen and (1-3C) alkyl; and / or Two Rs located on adjacent atoms 6 are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system, any of said monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; each p is independently selected from 0, 1, 2, or 3; R 7 are each independently selected from hydrogen or (1-3C) alkyl. The method is performed in the presence of

[0033] Upon detailed investigation, the present inventors have surprisingly discovered that a family of heterobimetallic catalysts represented by Formula I can catalyze the ROCOP of epoxides in the presence of CO to prepare polycarbonates such as PPC. The use of this novel family of catalysts in the ROCOP of epoxides represents a significant departure from the use of monometallic catalyst complexes in combination with cocatalysts, either in binary systems or as tethers to the ligand framework. The family of heterobimetallic catalysts described herein includes half-crown complexes of main group metals, transition metals, and lanthanides. Metal localization at crown-ether bonding sites is shown to result in both excellent activity and selectivity in the ROCOP of epoxides. Eliminating the need for a separate (or tethered) cocatalyst allows for greater control over the molar mass of the polymer, enabling the facile preparation of polycarbonates exhibiting monomodal molar mass distributions and controllable end groups. The kinetic studies described herein demonstrate that the copolymerization rate law is second order, linearly dependent on both epoxide monomer and catalyst concentrations, and zero-order dependent on CO pressure, allowing for the use of low pressure carbon dioxide (e.g., as low as 1 bar of CO). A thorough understanding of the rate laws demonstrating the polymerization methods of the present invention will facilitate future industrial optimization and scale-up.

[0034] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn. More preferably, M 1 is selected from Co, Fe, Cr, Ni, Al and Zn. Even more preferably, M 1 is selected from Co, Ni and Zn. 1 is Co.

[0035] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti, Zn and Mg. More preferably, M 1is selected from Co, Fe, Cr, Ni, Al, Zn and Mg. Even more preferably, M 1 is selected from Co, Ni, Zn and Mg. Most preferably, M 1 is Co.

[0036] In embodiments, M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn. More preferably, M 2 is selected from Na, K, Rb and Cs. Even more preferably, M 2 is K or Na. Optimally, M 2 is K.

[0037] In an embodiment, M1 is selected from Co, Fe, Cr, Ni, Al, Ti, Zn and Mg, and M2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0038] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn, and M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0039] In embodiments, M 1 is selected from Co, Fe, Cr, Ni and Zn, and M 2 is selected from Na, K, Rb and Cs.

[0040] In embodiments, M 1 is selected from Co, Ni and Zn, and M 2 is selected from Na, K, Rb and Cs.

[0041] In embodiments, M 1 is Co and M 2 is selected from Na, K, Rb and Cs.

[0042] In a particularly preferred embodiment, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, Cr and K, Al and K, Co and Ca, Co and Sr, or Co and Ba, respectively.

[0043] In a particularly preferred embodiment, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, or Cr and K, respectively.

[0044] In embodiments, R 1 is a (2-5C) alkylene, wherein 0, 1 or 2 carbon atoms in said (2-5C) alkylene are replaced by heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is replaced by one or more R x and optionally substituted independently by:

[0045] In embodiments, R x are respectively halo, hydroxy, cyano, nitro, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) haloalkyl, (1-10C) alkoxy, aryl, heteroaryl and -NR xa R xb are independently selected from R x Any of the aryl or heteroaryl groups in R is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy.

[0046] More preferably, R x are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x any of the phenyl or 5- to 6-membered heteroaryl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a 5- to 7-membered monocyclic or an 8- to 10-membered bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring system, any of said 5- to 7-membered monocyclic or 8- to 10-membered bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring systems optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy.

[0047] More preferably, R xare respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, wherein any of the benzene, cyclohexane, or naphthalene groups is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy.

[0048] In embodiments, R 1 has a structure according to Formula A shown below: [ka] and During the ceremony, W 1 , W 2 , W 3 , W 4 and W 5 are each independently selected from absent, —CH—, —NH—, and —O—; however, i)W 1 , W 2 , W 3 , W 4 and W 5 Three or fewer of these are not present, ii) W 1 , W 2, W 3 , W 4 and W 5 at least two of are -CH2-; iii) -NH- is not adjacent to -O-; Provided that, -CH2-, one or two R x and any one of -NH- is optionally substituted by one R x are substituted as necessary by

[0049] Preferably, W 1 , W 2 , W 3 , W 4 and W 5 At least three of the are -CH2-.

[0050] Preferably, W 1 , W 2 , W 3 , W 4 and W 5 are each independently selected from absent and -CH2-, and any of -CH2- is not present in one or two R x are substituted as necessary by

[0051] In embodiments, R 1 is one of the following structures: [ka] and During the ceremony, W 6 and W 7 Both are -O- or W 6 and W 7 are both -CH2-, and -CH2- is each selected from one or two R x and optionally independently substituted by W 8 is -O- or -NH-, and -NH- is R x and optionally substituted by Each q is 0, 1, or 2.

[0052] Preferably, W 6 and W 7 is -CH2-, each -CH2- is one R x and each independently may be substituted by:

[0053] Preferably, each q is 0 or 1.

[0054] In embodiments, R 1 is one of the following structures: [ka] and During the ceremony, R y are each independently selected from hydrogen, halo, cyano, (1-4C)alkyl, (1-4C)alkoxy, (1-4C)haloalkyl, phenyl, —NH and NMe; R z is selected from hydrogen and (1-2C) alkyl.

[0055] Preferably, R y are each independently selected from hydrogen, halo, cyano, (1-2C) alkyl, (1-2C) alkoxy, (1-2C) haloalkyl, phenyl, —NH and NMe; R z is selected from hydrogen and methyl.

[0056] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn, and M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn, and R 1 is one of the following structures: [ka] and During the ceremony, Ry are each independently selected from hydrogen, halo, cyano, (1-2C) alkyl, (1-2C) alkoxy, (1-2C) haloalkyl, phenyl, —NH and NMe; R z is selected from hydrogen and methyl.

[0057] In a particularly preferred embodiment, R 1 is one of the following structures: [ka] It has.

[0058] In a particularly preferred embodiment, R 1 is one of the following structures: [ka] It has.

[0059] X 1 The bond between R and N may be a single bond or a double bond. 2 If does not exist, X 1 The bond between R and N must be a double bond, and 2 If there is an X 1 It will be understood that the bond between and N is necessarily a single bond.

[0060] In embodiments, R 2 are respectively absent, hydrogen, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, phenyl, phenyl(1-2C) alkyl, 5-6 membered heteroaryl, 5-6 membered heteroaryl(1-2C) alkyl, and -C(O)-NR 2a R 2b are independently selected from R 2wherein any of the phenyl, phenyl(1-2C)alkyl, 5- to 6-membered heteroaryl, and 5- to 6-membered heteroaryl(1-2C)alkyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C)alkyl.

[0061] Preferably, R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C)alkyl.

[0062] More preferably, R 2 are absent, hydrogen, (1-3C) alkyl, phenyl, benzyl, and -C(O)-NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-2C)alkyl.

[0063] Even more preferably, R 2are absent, hydrogen, (1-3C) alkyl, phenyl, benzyl, and -C(O)-NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-2C)alkyl.

[0064] Even more preferably, R 2 are each independently selected from absent, hydrogen, and (1-2C)alkyl.

[0065] Optimally, R 2 are each independently selected from absent or hydrogen.

[0066] Preferably, R 2 are both the same.

[0067] X 1 -CH- or -CR 4 -If X 1 The bond between X and N must be a double bond, and 1 -CH2-, -CHR 4 -, -CR 4 R 4 - or -PR 4 R 4 -If X 1 It will be understood that the bond between and N is necessarily a single bond.

[0068] In embodiments, X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4independently selected from R 4 are each independently selected from (1-4C)alkyl, phenyl, and phenyl(1-2C)alkyl; R 4 wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy.

[0069] Preferably, X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 Any phenyl in is optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-2C)alkyl, (1-2C)haloalkyl and (1-2C)alkoxy.

[0070] More preferably, X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 Any phenyl in is optionally substituted by one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl and (1-2C)alkoxy.

[0071] Even more preferably, X 1 are -CH- and -CR 4-, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 are each independently (1-2C) alkyl.

[0072] Optimally, X 1 are each independently selected from -CH- or -CH2-.

[0073] Preferably, X 1 are both the same.

[0074] In embodiments, R 2 are absent, hydrogen, (1-3C) alkyl, phenyl, benzyl, and -C(O)-NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-2C) alkyl; X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 Any phenyl in is optionally substituted by one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl and (1-2C)alkoxy.

[0075] In embodiments, E 1 is C and E 2 is O, S or N, or E1 is N and E 2 is O. Optimally, E 1 is C and E 2 is O.

[0076] In embodiments, R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 3a , -C(O)-OR 3a , -OC(O)-R 3a , -C(O)-NR 3a R 3b , -N(R 3a )C(O)-R 3b and -NR 3a R 3b are independently selected from R 3 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C)alkyl.

[0077] Preferably, R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, 5-6 membered heteroaryl, 5-6 membered heteroaryl(1-2C) alkyl and -NR 3a R 3b are independently selected from R 3any of the aryl, aryl(1-2C)alkyl, 5- to 6-membered heteroaryl, and 5- to 6-membered heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C)alkyl.

[0078] More preferably, R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR 3a R 3b are independently selected from R 3 wherein any of the phenyl and 5- to 6-membered heteroaryl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C)alkyl.

[0079] Even more preferably, R 3 are halo, hydroxy, cyano, nitro, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, phenyl, and -NR 3a R 3b are independently selected from R 3 any phenyl in which is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C)alkyl.

[0080] Optimally, R 3are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C)alkyl.

[0081] Preferably, R 3 are all the same.

[0082] In embodiments, each n is independently selected from 0, 1, 2, and 3. Preferably, each n is independently selected from 0, 1, and 2. More preferably, each n is independently selected from 0 and 1. When n is 1, R 3 is preferably X 1 Optimally, n is 0 for each.

[0083] In embodiments, R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; each n is independently selected from 0 and 1; When n is 1, R 3 is preferably X 1 It is in the meta position.

[0084] L 1 , L 2 , G 1 and G 2 The existence, non-existence and properties of M 1 and M 2 It will be understood that the size and electronic configuration of the molecule will depend on the nature of the molecule (e.g., with respect to its size and electronic configuration).

[0085] L 1 and L2 For simplicity reasons, M 1 and M 2 Although Formula I shows each bond to only one of L 1 (and / or L 2 ) is M 1 and M 2 This binds to both M 1 and M 2 It will be appreciated that a bridge may be formed between L. 1 and L 2 Both of these are for single metals (e.g., M such as Co). 1 ) may be bonded solely to L 1 (and / or L 2 It will be further understood that L), when present, may bind to the metals of two different compounds of formula I, thus forming a bridge between the two compounds of formula I. Thus, multiple compounds of formula I may be bonded to their respective L 1 (and / or L 2 ) can be linked together in this way. The same theory, if it exists, 1 and G 2 applies to.

[0086] In an embodiment, L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-15C) alkyl, (2-15C) alkenyl, (2-15C) alkynyl, (1-15C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, heteroaryl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a, -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2 Any of the (1-15C) alkyl, (2-15C) alkenyl, (2-15C) alkynyl, (1-15C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl groups may contain one or more R b are substituted as necessary by

[0087] Preferably, L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, 5-6 membered heteroaryl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a, -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2 Any of the (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, and 5-6 membered heteroaryl may contain one or more R b are substituted as necessary by

[0088] In embodiments, R a are each independently selected from hydrogen, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl; R a Any (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl or heteroaryl occurring therein is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and (1-4C)alkoxy.

[0089] Preferably, R a are each independently selected from hydrogen, (1-6C) alkyl, (2-6C) alkenyl, (2-6C) alkynyl, (1-6C) heteroaliphatic, phenyl, and 5-6 membered heteroaryl; R aAny (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)heteroaliphatic, phenyl or 5-6 membered heteroaryl occurring therein is independently substituted by one or more groups independently selected from halo, amino, hydroxy, (1-2C)alkyl and (1-4C)alkoxy.

[0090] In embodiments, R b is each independently substituted with one or more groups independently selected from halo, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy.

[0091] In particular, L 1 and L 2 Non-limiting examples of include acetate, stearate, oleate, triflate (i.e., -OS(O)-CF), triflamide (i.e., -N(H)-S(O)-CF), triflimide (i.e., -N-(S(O)-CF)), and xanthate (e.g., -SC(S)-O-CH). In any of these cases, L 1 and L 2 may also be independently selected from O-benzoyl (ie, "OBz").

[0092] In a particularly preferred embodiment, L 1 and L 2 does not exist and -OC(O)-R a are independently selected from R a is (1-20C) alkyl (e.g., acetate, i.e., "OAc" or stearate) or (2-25C) alkenyl (e.g., oleate). 1 and L 2 is independently selected from absent and acetate. In either of these cases, L 1 and L 2 may also be independently selected from O-benzoyl (ie, "OBz").

[0093] In an embodiment, G 1 and G 2 are each independently selected from absent, a Lewis base, and a solvent (e.g., water or an alcohol).

[0094] In a particularly preferred embodiment, G 1 and G 2 does not exist.

[0095] L 1 , L 2 , G 1 and G 2 Except for the one or more additional ligands, depending on their size and electron configuration, e.g., M 1 and / or M 2 It will be understood that the hydroxyl group may or may not be coordinated to the hydroxyl group.

[0096] In embodiments, X 2 are each independently absent or (1-2C)alkylene, said (1-2C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl. 2 are each independently absent or methylene, said methylene being optionally substituted with one or two groups independently selected from (1-2C) alkyl. More preferably, X 2 are each independently absent or methylene, said methylene being optionally substituted with one or two methyl groups. 2 Each is independently absent or methylene.

[0097] Preferably, X 2 are both the same.

[0098] In embodiments, X 3are each independently absent or (1-2C)alkylene, said (1-2C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl. 3 are each independently absent or methylene, said methylene being optionally substituted with one or two groups independently selected from (1-2C) alkyl. More preferably, X 3 are each independently absent or methylene, said methylene being optionally substituted with one or two methyl groups. 3 Each is independently absent or methylene.

[0099] Preferably, X 3 are both the same.

[0100] In embodiments, X 4 Each X is independently methylene optionally substituted with one or two methyl groups. 4 are each methylene.

[0101] Preferably, X 4 are both the same.

[0102] In embodiments, X 2 each independently is absent or methylene, said methylene being optionally substituted with one or two groups independently selected from (1-2C)alkyl; X 3 each independently is absent or methylene, said methylene being optionally substituted with one or two groups independently selected from (1-2C)alkyl; X 4 Each is independently methylene optionally substituted with one or two methyl groups.

[0103] In embodiments, m is 1, 2 or 3. Most preferably, m is 2.

[0104] In embodiments, R 5 are respectively hydrogen, halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, phenyl(1-2C) alkyl, 5-6 membered heteroaryl, 5-6 membered heteroaryl(1-2C) alkyl and -NR 5a R 5b are independently selected from R 5 wherein any of the phenyl, phenyl(1-2C)alkyl, 5- to 6-membered heteroaryl, and 5- to 6-membered heteroaryl(1-2C)alkyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-3C) alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other such that, when taken together with the atoms to which they are attached, they form benzene, a 5- to 6-membered heteroaromatic ring, a 5- to 6-membered carbocyclic ring, or a 5- to 6-membered heterocyclic ring, any of which is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy.

[0105] Preferably, R 5 are respectively hydrogen, halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, phenyl(1-2C) alkyl and -NR 5a R 5b are independently selected from R 5wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-2C) alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other such that, when taken together with the atoms to which they are attached, they form benzene, a 5- to 6-membered heteroaromatic ring, a 5- to 6-membered carbocyclic ring, or a 5- to 6-membered heterocyclic ring, any of which is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy.

[0106] More preferably, R 5 are respectively hydrogen, halo, hydroxy, (1-3C) alkyl, (1-3C) haloalkyl, (1-3C) alkoxy, phenyl, phenyl(1-2C) alkyl and -NR 5a R 5b are independently selected from R 5 wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-2C) alkyl; and / or two Rs located on adjacent atoms 5are linked to each other such that, when taken together with the atoms to which they are attached, they form a benzene or a 5- to 6-membered heteroaromatic ring, both of which are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy.

[0107] Even more preferably, R 5 are each independently selected from hydrogen and (1-2C) alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other such that, when taken together with the atoms to which they are attached, they form a benzene ring, optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy.

[0108] More preferably, R 5 are each independently selected from hydrogen and (1-2C)alkyl.

[0109] In embodiments, R 6 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 6a , -C(O)-OR 6a , -OC(O)-R 6a , -C(O)-NR 6a R 6b , -N(R 6a )C(O)-R 6b and -NR 6a R 6b are independently selected from R 6wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 6a and R 6b are independently selected from hydrogen and (1-3C)alkyl.

[0110] Preferably, R 6 are halo, hydroxy, cyano, nitro, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, phenyl, and -NR 6a R 6b are independently selected from R 6 any phenyl in which is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 6a and R 6b are independently selected from hydrogen and (1-3C)alkyl.

[0111] More preferably, R 6 are halo, cyano, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 6a R 6b are independently selected from R 6a and R 6b are independently selected from hydrogen and (1-2C)alkyl.

[0112] Even more preferably, R 6 are halo, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 6a R 6b are independently selected from R 6a and R 6b is independently selected from hydrogen and methyl.

[0113] Optimally, R 6 are each independently selected from halo, methyl and methoxy.

[0114] In embodiments, each p is independently selected from 0, 1, or 2. Most preferably, each p is independently selected from 0 and 1. Suitably, when p is 1, R 6 -OR 7 It is in the para rank.

[0115] In embodiments, R 7 are each independently selected from hydrogen or (1-2C) alkyl. 7 are each independently selected from hydrogen or methyl. Even more preferably, R 7 are each methyl.

[0116] In embodiments, R 5 are respectively hydrogen, halo, hydroxy, (1-3C) alkyl, (1-3C) haloalkyl, (1-3C) alkoxy, phenyl, phenyl(1-2C) alkyl and -NR 5a R 5b are independently selected from R 5 wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-2C) alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene or a 5- to 6-membered heteroaromatic ring, any of said benzene and 5- to 6-membered heteroaromatic rings being optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl and (1-2C)alkoxy; R 6are halo, cyano, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 6a R 6b are independently selected from R 6a and R 6b are independently selected from hydrogen and (1-2C) alkyl; each p is independently selected from 0 and 1; R 7 are each independently selected from hydrogen or methyl.

[0117] Formula I is a group in which Q is M 2 It will be understood that this is a schematic diagram illustrating how the M 2 Depending on the nature of Q (in terms of its size and electron configuration), Q may be linked to M via three or more oxygen atoms in Q as outlined in the accompanying examples. 2 can be combined with

[0118] In a particularly preferred embodiment, Q is QI.

[0119] In particularly preferred embodiments, Q has a structure according to any of the following: [ka] and In the formula, R 6 and R 7 Each independently has any of the definitions appearing earlier in this specification. 6 are each independently halo, methyl, and methoxy; R 7 is each independently hydrogen or methyl.

[0120] In a more preferred embodiment, Q has the structure: [ka] It has.

[0121] In an even more preferred embodiment, Q has the structure: [ka] It has.

[0122] In certain embodiments, the compound of Formula I has a structure according to Formula II, shown below, which is a partial definition of Formula I: [ka] (In the formula, M 1 , M 2 , R 1 , R 2 , R 3 , R 5 , X 1 , X 2 , E 1 , E 2 , L 1 , L 2 , G 1 , G 2 , m, n, and any moieties related thereto have any of the definitions outlined earlier in this specification and / or appearing in the following embodiments.

[0123] In an embodiment, M1 is selected from Co, Fe, Cr, Ni, Al, Ti, Zn and Mg, and M2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0124] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn, and M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0125] In embodiments, M 1 is selected from Co, Fe, Cr, Ni and Zn, and M 2 is selected from Na, K, Rb and Cs.

[0126] In embodiments, M 1 is Co and M 2 is selected from Na, K, Rb and Cs.

[0127] In embodiments, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, Cr and K, Al and K, Co and Ca, Co and Sr, or Co and Ba, respectively.

[0128] In embodiments, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, or Cr and K, respectively.

[0129] In embodiments, R 1 is a (2-5C) alkylene, wherein 0, 1 or 2 carbon atoms in said (2-5C) alkylene are replaced by heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is replaced by one or more R x and optionally substituted independently by R x are respectively halo, hydroxy, cyano, nitro, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) haloalkyl, (1-10C) alkoxy, aryl, heteroaryl and -NR xa R xb are independently selected from R x Any of the aryl or heteroaryl groups in R is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy;xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy.

[0130] In embodiments, R 1 is a (2-5C) alkylene, wherein 0, 1 or 2 carbon atoms in said (2-5C) alkylene are replaced by heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is replaced by one or more R x and optionally substituted independently by R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms xare linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, wherein any of the benzene, cyclohexane, or naphthalene groups is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy.

[0131] In embodiments, R 1 is one of the following structures: [ka] [ka] and During the ceremony, W 6 and W 7 Both are -O- or W 6 and W 7 are both -CH2-, and -CH2- is each selected from one or two R x and optionally independently substituted by W 8 is -O- or -NH-, and -NH- is R x and optionally substituted by Each q is 0, 1, or 2.

[0132] In embodiments, R 1 is one of the following structures: [ka] It has.

[0133] In embodiments, R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl. 2 are each independently selected from absent, hydrogen, and (1-2C)alkyl.

[0134] In embodiments, E 1 is C and E 2 is O.

[0135] In embodiments, X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 Any phenyl in is optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-2C) alkyl, (1-2C) haloalkyl and (1-2C) alkoxy. 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 are each independently (1-2C) alkyl.

[0136] In embodiments, R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR3a R 3b are independently selected from R 3 wherein any of the phenyl and 5- to 6-membered heteroaryl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl. 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b is independently selected from hydrogen and (1-3C)alkyl. In such embodiments, each n is independently selected from 0, 1 and 2. Suitably, each n is independently 0 or 1.

[0137] In an embodiment, L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, 5-6 membered heteroaryl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a, -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2 Any of the (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, and 5-6 membered heteroaryl may contain one or more R b and R a are each independently selected from hydrogen, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl; R a any (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl, or heteroaryl occurring therein is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy;

[0138] R b is each independently substituted with one or more groups independently selected from halo, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy.

[0139] In an embodiment, L 1 and L 2 does not exist and -OC(O)-R a are independently selected from R ais (1-20C) alkyl (e.g., acetate, i.e., "OAc" or stearate) or (2-25C) alkenyl (e.g., oleate). 1 and L 2 does not exist and -OC(O)-R a are independently selected from R a is (1-12C) alkyl. 1 and L 2 does not exist and -OC(O)-R a are independently selected from R a is (1-6) alkyl. In particularly preferred embodiments, L 1 and L 2 is independently selected from absent and acetate. In either of these cases, L 1 and L 2 may also be independently selected from O-benzoyl (ie, "OBz").

[0140] In an embodiment, G 1 and G 2 does not exist.

[0141] In embodiments, X 2 are each independently absent or methylene, said methylene being optionally substituted with one or two groups independently selected from (1-2C) alkyl. 2 Each is independently absent or methylene.

[0142] In an embodiment, m is 2.

[0143] In embodiments, R 5 are respectively hydrogen, halo, hydroxy, (1-3C) alkyl, (1-3C) haloalkyl, (1-3C) alkoxy, phenyl, phenyl(1-2C) alkyl and -NR 5a R 5b are independently selected from R 5wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-2C) alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other such that, when taken together with the atoms to which they are attached, they form a benzene or a 5- to 6-membered heteroaromatic ring, both of which are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy. 5 are each independently selected from hydrogen and (1-2C)alkyl.

[0144] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; R 1 is one of the following structures: [ka] and During the ceremony, W 6 and W 7 Both are -O- or W 6 and W 7 are both -CH2-, and -CH2- is each selected from one or two R x and optionally independently substituted by W 8 is -O- or -NH-, and -NH- is R x and optionally substituted by q is 0, 1, or 2, and R 2 is independently selected from absent, hydrogen and (1-2C)alkyl; R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, any of said benzene, cyclohexane, or naphthalene groups being optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; each n is independently selected from 0, 1, and 2; m is 2.

[0145] In embodiments, M 1 is selected from Co, Ni and Zn; M 2 is selected from Na, K, Rb and Cs; R 1 is one of the following structures: [ka] and R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl; E 1 is C and E 2 is O, R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; each n is independently selected from 0, 1, and 2; X 2 each independently is absent or methylene; R 5 are respectively hydrogen, halo, hydroxy, (1-3C) alkyl, (1-3C) haloalkyl, (1-3C) alkoxy, phenyl, phenyl(1-2C) alkyl and -NR 5a R 5b are independently selected from R 5wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-2C) alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene or a 5- to 6-membered heteroaromatic ring, any of said benzene and 5- to 6-membered heteroaromatic rings being optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl and (1-2C)alkoxy; m is 2.

[0146] In certain embodiments, the compound of Formula I has a structure according to Formulas I-II shown below, which are subdefinitions of Formula I: [ka] (In the formula, M 1 , M 2 , R 1 , R 2 , R 3 , L 1 , L 2 , G 1 , G 2 , Q and any moieties associated therewith have any of the definitions outlined earlier in this specification and / or appearing in the following embodiments).

[0147] In an embodiment, M1 is selected from Co, Fe, Cr, Ni, Al, Ti, Zn and Mg, and M2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0148] In embodiments, M 1is selected from Co, Fe, Cr, Ni, Al, Ti and Zn, and M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0149] In embodiments, M 1 is selected from Co, Fe, Cr, Ni and Zn, and M 2 is selected from Na, K, Rb and Cs.

[0150] In embodiments, M 1 is Co and M 2 is selected from Na, K, Rb and Cs.

[0151] In embodiments, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, Cr and K, Al and K, Co and Ca, Co and Sr, or Co and Ba, respectively.

[0152] In embodiments, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, or Cr and K, respectively.

[0153] In embodiments, R 1 is a (2-5C) alkylene, wherein 0, 1 or 2 carbon atoms in said (2-5C) alkylene are replaced by heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is replaced by one or more R x and optionally substituted independently by R xare respectively halo, hydroxy, cyano, nitro, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) haloalkyl, (1-10C) alkoxy, aryl, heteroaryl and -NR xa R xb are independently selected from R x Any of the aryl or heteroaryl groups in R is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy.

[0154] In embodiments, R 1 is a (2-5C) alkylene, wherein 0, 1 or 2 carbon atoms in said (2-5C) alkylene are replaced by heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is replaced by one or more R x and optionally substituted independently by R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R xAny of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, wherein any of the benzene, cyclohexane, or naphthalene groups is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy.

[0155] In embodiments, R 1 is one of the following structures: [ka] and During the ceremony, W 6 and W 7 Both are -O- or W 6 and W 7 are both -CH2-, and -CH2- is each selected from one or two R x and optionally independently substituted by W 8 is -O- or -NH-, and -NH- is R x and optionally substituted by Each q is 0, 1, or 2.

[0156] In embodiments, R 1 is one of the following structures: [ka] It has.

[0157] In embodiments, R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl. 2 are each independently selected from absent, hydrogen, and (1-2C)alkyl.

[0158] In embodiments, R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR 3a R 3b are independently selected from R 3 wherein any of the phenyl and 5- to 6-membered heteroaryl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl. 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C)alkyl.

[0159] In an embodiment, L1 and L 2 is absent, halo, nitrate, hydroxy, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, 5-6 membered heteroaryl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2 Any of the (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, and 5-6 membered heteroaryl may contain one or more R b and R a are each independently selected from hydrogen, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl; R aany (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl, or heteroaryl occurring therein is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; R b is each independently substituted with one or more groups independently selected from halo, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy.

[0160] In an embodiment, L 1 and L 2 does not exist and -OC(O)-R a are independently selected from R a is (1-20C) alkyl (e.g., acetate, i.e., "OAc" or stearate) or (2-25C) alkenyl (e.g., oleate). In either of these cases, L 1 and L 2 may also be independently selected from O-benzoyl (ie, "OBz").

[0161] In an embodiment, G 1 and G 2 does not exist.

[0162] In embodiments, Q has a structure according to any one of the following: [ka] and In the formula, R 6 are each independently halo, methyl, and methoxy; R 7 is each independently hydrogen or methyl.

[0163] In embodiments, M 1is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; R 1 is one of the following structures: [ka] [ka] and During the ceremony, W 6 and W 7 Both are -O- or W 6 and W 7 are both -CH2-, and -CH2- is each selected from one or two R x and optionally independently substituted by W 8 is -O- or -NH-, and -NH- is R x and optionally substituted by q is 0, 1, or 2, and R 2 is independently selected from absent, hydrogen and (1-2C)alkyl; R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms xare linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, any of said benzene, cyclohexane, or naphthalene groups being optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C)alkyl.

[0164] In embodiments, M 1 is selected from Co, Ni and Zn; M 2 is selected from Na, K, Rb and Cs; R 1 is one of the following structures: [ka] and R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl; R 3are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; Q is one of the following structures: [ka] and In the formula, R 6 are each independently halo, methyl, and methoxy; R 7 is each independently hydrogen or methyl.

[0165] In certain embodiments, the compound of Formula I has a structure according to Formulas I-III shown below, which are subdefinitions of Formula I: [ka] and In the formula, M 1 , M 2 , X 1 , R 2 , R 3 , E 2 , L 1 , L 2 , G 1 , G 2 , n, Q, W 1 , W 2 , W 3 , W 4 , W 5 and any moieties associated therewith have any of the definitions outlined earlier in this specification and / or appearing in the following embodiments.

[0166] In an embodiment, W 1 , W 2 , W 3 , W 4 and W 5 are each independently selected from absent and -CH2-, and any of -CH2- is not present in one or two Rx Preferably, R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, wherein any of the benzene, cyclohexane, or naphthalene groups is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy.

[0167] In embodiments, the group: [ka] is one of the following structures: [ka] and In the formula, R y and R z is as defined herein. Preferably, R y are each independently selected from hydrogen, halo, cyano, (1-2C) alkyl, (1-2C) alkoxy, (1-2C) haloalkyl, phenyl, —NH and NMe; R z is selected from hydrogen and methyl.

[0168] In embodiments, X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 Any phenyl in is optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-2C) alkyl, (1-2C) haloalkyl and (1-2C) alkoxy. 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 are each independently (1-2C) alkyl.

[0169] In an embodiment, M1 is selected from Co, Fe, Cr, Ni, Al, Ti, Zn and Mg, and M2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0170] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0171] In embodiments, M 1 is selected from Co, Fe, Cr, Ni and Zn; M 2 is selected from Na, K, Rb and Cs.

[0172] In embodiments, M 1 is Co and M 2 is selected from Na, K, Rb and Cs.

[0173] In embodiments, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, Cr and K, Al and K, Co and Ca, Co and Sr, or Co and Ba, respectively.

[0174] In embodiments, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, or Cr and K, respectively.

[0175] In embodiments, E 2 is O.

[0176] In embodiments, R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl. 2 are each independently selected from absent, hydrogen, and (1-2C)alkyl.

[0177] In embodiments, R 3are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR 3a R 3b are independently selected from R 3 wherein any of the phenyl and 5- to 6-membered heteroaryl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl. 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b is independently selected from hydrogen and (1-3C)alkyl. In such embodiments, each n is independently selected from 0, 1 and 2. Suitably, each n is independently 0 or 1.

[0178] In an embodiment, L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, 5-6 membered heteroaryl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-Ra (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2 Any of the (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, and 5-6 membered heteroaryl may contain one or more R b and R a are each independently selected from hydrogen, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl; R a any (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl, or heteroaryl occurring therein is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; R b is each independently substituted with one or more groups independently selected from halo, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy.

[0179] In an embodiment, L 1 and L 2does not exist and -OC(O)-R a are independently selected from R a is (1-20C) alkyl (e.g., acetate, i.e., "OAc" or stearate) or (2-25C) alkenyl (e.g., oleate). In either of these cases, L 1 and L 2 may also be independently selected from O-benzoyl (ie, "OBz").

[0180] In an embodiment, G 1 and G 2 does not exist.

[0181] In embodiments, Q has a structure according to any one of the following: [ka] and In the formula, R 6 are each independently halo, methyl, and methoxy; R 7 is each independently hydrogen or methyl.

[0182] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; W 1 , W 2 , W 3 , W 4 and W 5 are each independently selected from absent and -CH2-, and any of -CH2- is not present in one or two R x and R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xbare independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, any of said benzene, cyclohexane, or naphthalene groups being optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; E 2 is O, R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl; X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4are each independently selected from (1-2C) alkyl and phenyl; R 4 wherein any phenyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; each n is independently selected from 0, 1, and 2; Q is one of the following structures: [ka] and In the formula, R 6 are each independently halo, methyl, and methoxy; R 7 is each independently hydrogen or methyl.

[0183] In embodiments, M 1 is selected from Co, Ni and Zn; M 2 is selected from Na, K, Rb and Cs; Base: [ka] is one of the following structures: [ka] and In the formula, R y are each independently selected from hydrogen, halo, cyano, (1-2C) alkyl, (1-2C) alkoxy, (1-2C) haloalkyl, phenyl, —NH and NMe; R zis selected from hydrogen and methyl; X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 wherein any phenyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl; R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; each n is independently selected from 0, 1, and 2; Q is one of the following structures: [ka] and In the formula, R 6 are each independently halo, methyl, and methoxy; R 7 is each independently hydrogen or methyl.

[0184] In certain embodiments, the compound of Formula I has a structure according to Formulas I-IV shown below, which are subdefinitions of Formula I: [ka] and In the formula, M 1 , M 2 , X 1 , E 1 , E 2 , R 1 , R 2 , R 3 , L 1 , L 2 , G 1 , G 2 , n, and any moieties related thereto have any of the definitions outlined earlier in this specification and / or appearing in the following embodiments.

[0185] In an embodiment, M1 is selected from Co, Fe, Cr, Ni, Al, Ti, Zn and Mg, and M2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0186] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0187] In embodiments, M 1 is selected from Co, Fe, Cr, Ni and Zn; M 2 is selected from Na, K, Rb and Cs.

[0188] In embodiments, M 1 is Co and M 2 is selected from Na, K, Rb and Cs.

[0189] In embodiments, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, Cr and K, Al and K, Co and Ca, Co and Sr, or Co and Ba, respectively.

[0190] In embodiments, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, or Cr and K, respectively.

[0191] In embodiments, R 1 is a (2-5C) alkylene, wherein 0, 1 or 2 carbon atoms in said (2-5C) alkylene are replaced by heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is replaced by one or more R x and optionally substituted independently by R x are respectively halo, hydroxy, cyano, nitro, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) haloalkyl, (1-10C) alkoxy, aryl, heteroaryl and -NR xa R xb are independently selected from R x Any of the aryl or heteroaryl groups in R is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy;xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy.

[0192] In embodiments, R 1 is a (2-5C) alkylene, wherein 0, 1 or 2 carbon atoms in said (2-5C) alkylene are replaced by heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is replaced by one or more R x and optionally substituted independently by R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms xare linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, wherein any of the benzene, cyclohexane, or naphthalene groups is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy.

[0193] In embodiments, R 1 is one of the following structures: [ka] [ka] and During the ceremony, W 6 and W 7 Both are -O- or W 6 and W 7 are both -CH2-, and -CH2- is each selected from one or two R x and optionally independently substituted by W 8 is -O- or -NH-, and -NH- is R x and optionally substituted by Each q is 0, 1, or 2.

[0194] In embodiments, R 1 is one of the following structures: [ka] It has.

[0195] In embodiments, X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 Any phenyl in is optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-2C) alkyl, (1-2C) haloalkyl and (1-2C) alkoxy. 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 are each independently (1-2C) alkyl.

[0196] In embodiments, R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl. 2 are each independently selected from absent, hydrogen, and (1-2C)alkyl.

[0197] In embodiments, R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR 3a R 3b are independently selected from R 3wherein any of the phenyl and 5- to 6-membered heteroaryl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl. 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b is independently selected from hydrogen and (1-3C)alkyl. In such embodiments, each n is independently selected from 0, 1 and 2. Suitably, each n is independently 0 or 1.

[0198] In embodiments, E 1 is C and E 2 is O.

[0199] In an embodiment, L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, 5-6 membered heteroaryl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2 Any of the (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, and 5-6 membered heteroaryl may contain one or more R b and R a are each independently selected from hydrogen, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl; R a any (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl, or heteroaryl occurring therein is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; R b is each independently substituted with one or more groups independently selected from halo, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy.

[0200] In an embodiment, L 1 and L 2 does not exist and -OC(O)-R a are independently selected from R ais (1-20C) alkyl (e.g., acetate, i.e., "OAc" or stearate) or (2-25C) alkenyl (e.g., oleate). In either of these cases, L 1 and L 2 may also be independently selected from O-benzoyl (ie, "OBz").

[0201] In an embodiment, G 1 and G 2 does not exist.

[0202] In embodiments, M 1 is selected from Co, Ni and Zn; M 2 is selected from Na, K, Rb and Cs; R 1 is one of the following structures: [ka] and In the formula, R y are each independently selected from hydrogen, halo, cyano, (1-2C) alkyl, (1-2C) alkoxy, (1-2C) haloalkyl, phenyl, —NH and NMe; R z is selected from hydrogen and methyl; X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 wherein any phenyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; L 1 and L 2does not exist and -OC(O)-R a are independently selected from R a is (1-6C) alkyl (e.g. acetate) or (2-25C) alkenyl (e.g. stearate or oleate), R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; Each n is independently selected from 0, 1 and 2.

[0203] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; R 1 is one of the following structures: [ka] and X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 are each independently (1-2C) alkyl; R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl; E 1 is C and E 2 is O, R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; Each n is independently selected from 0 and 1.

[0204] In certain embodiments, the compound of Formula I has a structure according to Formula IV, shown below, which is a partial definition of Formula I: [ka] and In the formula, M 1 , M 2 , R 2 , R 3 , E 1 , E 2 , L 1 , L 2 , G 1 , G 2 , W 1 , W 2 , W 3 , W 4 , W 5 , n, and any moieties related thereto have any of the definitions outlined earlier in this specification and / or appearing in the following embodiments.

[0205] In an embodiment, W 1 , W 2 , W3 , W 4 and W 5 are each independently selected from absent and -CH2-, and any of -CH2- is not present in one or two R x Preferably, R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, wherein any of the benzene, cyclohexane, or naphthalene groups is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy.

[0206] In embodiments, the group: [ka] is one of the following structures: [ka] and In the formula, R y and R z is as defined herein. Preferably, R yare each independently selected from hydrogen, halo, cyano, (1-2C) alkyl, (1-2C) alkoxy, (1-2C) haloalkyl, phenyl, —NH and NMe; R z is selected from hydrogen and methyl.

[0207] In an embodiment, M1 is selected from Co, Fe, Cr, Ni, Al, Ti, Zn and Mg, and M2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0208] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn.

[0209] In embodiments, M 1 is selected from Co, Fe, Cr, Ni and Zn; M 2 is selected from Na, K, Rb and Cs.

[0210] In embodiments, M 1 is Co and M 2 is selected from Na, K, Rb and Cs.

[0211] In embodiments, M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, Cr and K, Al and K, Co and Ca, Co and Sr, or Co and Ba, respectively.

[0212] In embodiments, M 1 and M 2are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, or Cr and K, respectively.

[0213] In embodiments, R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl. 2 are each independently selected from absent, hydrogen, and (1-2C)alkyl.

[0214] In embodiments, E 1 is C and E 2 is O.

[0215] In embodiments, R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR 3a R 3b are independently selected from R 3 wherein any of the phenyl and 5- to 6-membered heteroaryl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl. 3are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b is independently selected from hydrogen and (1-3C)alkyl. In such embodiments, each n is independently selected from 0, 1 and 2. Suitably, each n is independently 0 or 1.

[0216] In an embodiment, L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, 5-6 membered heteroaryl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2Any of the (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, and 5-6 membered heteroaryl may contain one or more R b and R a are each independently selected from hydrogen, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl; R a any (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl, or heteroaryl occurring therein is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; R b is each independently substituted with one or more groups independently selected from halo, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy.

[0217] In an embodiment, L 1 and L 2 does not exist and -OC(O)-R a are independently selected from R a is (1-20C) alkyl (e.g., acetate, i.e., "OAc" or stearate) or (2-25C) alkenyl (e.g., oleate). In either of these cases, L 1 and L 2 may also be independently selected from O-benzoyl (ie, "OBz").

[0218] In an embodiment, G 1 and G 2 does not exist.

[0219] In an embodiment, W 1 , W 2 , W 3 , W 4 and W 5 are each independently selected from absent and -CH2-, and any of -CH2- is not present in one or two R x and R 2 are respectively absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl; R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; Each n is independently selected from 0, 1 and 2.

[0220] In embodiments, M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; Base: [ka] is one of the following structures: [ka] and In the formula, R y are each independently selected from hydrogen, halo, cyano, (1-2C) alkyl, (1-2C) alkoxy, (1-2C) haloalkyl, phenyl, —NH and NMe; R z is selected from hydrogen and methyl; R 2 are each independently selected from absent, hydrogen, and (1-2C)alkyl; E 1 is C and E 2 is O, R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; Each n is independently selected from 0, 1 and 2.

[0221] In certain embodiments, the compound of Formula I has a structure according to Formulas I-VI shown below, which are partial definitions of Formula I: [ka] and In the formula, M 1 , M 2 , R 1 , R 2 , L 1 , L 2 and any moieties associated therewith have any of the definitions outlined earlier in this specification and / or appearing in the following embodiments.

[0222] In embodiments, R 1 is one of the following structures: [ka] and M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; L 1 and L 2 has any of the definitions appearing earlier in this specification. 1 and L 2 At least one of the is acetate and the other is acetate or is absent.

[0223] In embodiments, R 1 is one of the following structures: [ka] and M 1 is selected from Co, Fe, Cr, Ni, Al, Ti, Zn and Mg; M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; L 1 and L 2 has any of the definitions appearing earlier in this specification. 1 and L 2 At least one of the is acetate and the other is acetate or is absent.

[0224] In embodiments, R 1 is one of the following structures: [ka] and M 1 and M 2are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, or Cr and K, respectively; L 1 and L 2 has any of the definitions appearing earlier in this specification. 1 and L 2 At least one of the is acetate and the other is acetate or is absent.

[0225] In embodiments, R 1 is one of the following structures: [ka] and M 1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, Cr and K, Al and K, Co and Ca, Co and Sr, or Co and Ba, respectively; L 1 and L 2 has any of the definitions appearing earlier in this specification. 1 and L 2 At least one of the is acetate and the other is acetate or is absent.

[0226] In certain embodiments, the compound of formula I has a structure according to any of the following: [ka] [ka] [ka] (In the formula, L 1and L 2 is present and has any of the definitions appearing earlier in this specification). 1 and L 2 is acetate. L in any of the structures illustrated throughout this specification 1 and L 2 It will be understood that L can adopt any of the configurations described anywhere herein. For example, L 1 and L 2 are, respectively, M 1 and M 2 Sometimes only one of the two is bound to L. 1 (and / or L 2 ) is also M 1 and M 2 and L 1 and L 2 Both of these are for single metals (e.g., M such as Co). 1 ) may be bonded solely to L 1 (and / or L 2 ), when present, can bind to the metals of two different compounds of formula I, thus forming a bridge between the two compounds of formula I. Thus, multiple compounds of formula I can be bonded to their respective L 1 (and / or L 2 ) can be linked together in this way. The same theory, if it exists, 1 and G 2 applies to.

[0227] In certain embodiments, the compound of formula I has a structure according to any one of the following: [ka] [ka] [ka] [ka] (In the formula, L 1 , L 2 and G 1 is present and has any of the definitions appearing earlier in this specification). 1 , L 2 and G 1 is acetate or O-benzoyl.

[0228] In certain embodiments, the compound of formula I has a structure according to any one of the following: [ka] [ka] [ka] (In the formula, L 1 , L 2 and G 1 is present and has any of the definitions appearing earlier in this specification). 1 , L 2 and G 1 is acetate or O-benzoyl.

[0229] Suitably, the compound of formula I has a structure according to any of the following: [ka] [ka] (In the formula, L 1 and L 2 and G 1 is present and has any of the definitions appearing earlier in this specification). 1 and L 2 is acetate or O-benzoyl.

[0230] The process of the first aspect of the invention is the ROCOP process, in which an epoxide is copolymerized with CO2 to form a polycarbonate. Polycarbonate can be viewed as an alternating copolymer of ring-opened epoxide and CO2.

[0231] In an embodiment, in step a), the compound of formula I is present in an amount of 0.0001 to 0.5 mol % relative to the number of moles of epoxide. Preferably, in step a), the compound of formula I is present in an amount of 0.001 to 0.3 mol % relative to the number of moles of epoxide. More preferably, in step a), the compound of formula I is present in an amount of 0.01 to 0.1 mol % relative to the number of moles of epoxide. Even more preferably, in step a), the compound of formula I is present in an amount of 0.015 to 0.05 mol % relative to the number of moles of epoxide. Even more preferably, in step a), the compound of formula I is present in an amount of 0.025 mol % relative to the number of moles of epoxide.

[0232] The polymerization is preferably carried out in a solution of the epoxide (i.e., the epoxide dissolved in a suitable solvent) or in the absence of a solvent under a gaseous flow of CO. More preferably, the polymerization process is carried out in the absence of a solvent under a gaseous flow of CO.

[0233] The term "epoxide," as used herein, refers to any compound containing an epoxide moiety. An epoxide substrate may contain more than one epoxide moiety, i.e., a bis-epoxide, tris-epoxide, or multi-epoxide-containing moiety. It is understood that reactions carried out in the presence of one or more compounds having more than one epoxide moiety may result in crosslinking of the resulting polymer. It is understood that the term "epoxide" is intended to encompass one or more epoxides. In other words, the term "epoxide" may refer to a single epoxide or a mixture of two or more different epoxides.

[0234] In embodiments, the epoxide is located on a group that is cyclic or acyclic.

[0235] In embodiments, the epoxides are cyclohexene oxide, styrene oxide, alkylene oxides (such as ethylene oxide, propylene oxide, vinyl-propylene oxide, and butylene oxide), cyclohexene oxide (limonene oxide, C 10 H 16 O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and C 11 H 22 O, etc.), oxiranes (oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyloxirane, 2-(2-(2-methoxyethoxy)ethoxy)methyloxirane, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyloxirane, etc.), 1,2-epoxybutane, glycidyl ethers (allyl glycidyl ether, tert-butyl glycidyl ether, glycidyl methyl ether, isopropyl glycidyl ether, butyl glycidyl ether, methoxyethyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, m-tolyl glycidyl ether, glycidyl propargyl ether, beta-chloroethyl glycidyl ether, fulvic acid, The epoxy groups are selected from the group consisting of tetrahydrofurfuryl glycidyl ether, tetrahydrofurfuryl glycidyl ether, glycidyl esters (such as glycidyl benzoate), glycidyl carbonates (such as methyl glycidyl carbonate, ethyl glycidyl carbonate, and chloestryl glycidyl carbonate), vinylcyclohexene oxide, 3-phenyl-1,2-epoxypropane, 1,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide, THF-epoxides, and functionalized 3,5-dioxaepoxides, and mixtures of two or more thereof. It will be understood that any of the foregoing epoxides may be substituted or unsubstituted.

[0236] Preferably, the epoxide is selected from ethylene oxide, propylene oxide, vinyl-propylene oxide, butylene oxide, allyl glycidyl ether, tert-butyl glycidyl ether, epichlorohydrin, styrene oxide, cyclohexene oxide, vinyl-cyclohexene oxide, cyclopentene oxide, limonene oxide, and mixtures of two or more thereof.

[0237] In particularly preferred embodiments, the epoxide is propylene oxide or cyclohexene oxide.

[0238] In particularly preferred embodiments, the epoxide is propylene oxide. In such embodiments, the product of the polymerization process is polypropylene carbonate.

[0239] The catalytic process for preparing polycarbonates according to the first aspect of the present invention may optionally be carried out in the presence of a chain transfer agent. The catalysts described herein are highly tolerant to chain transfer agents, allowing for easy utilization of polyols.

[0240] In an embodiment, step a) is carried out in the presence of a chain transfer agent. Suitable chain transfer agents will be familiar to those skilled in the art.

[0241] The chain transfer agent can be water or a compound having one or more groups independently selected from hydroxy, amino and thiol.

[0242] In embodiments, the chain transfer agent is selected from the group consisting of water, a monoalcohol, a diol, a triol, a tetraol, a polyol, a monoamine, a polyamine, a monothiol, a polythiol, a monocarboxylic acid, or a polycarboxylic acid. In embodiments, the chain transfer agent is selected from the group consisting of water, monoalcohols (i.e., alcohols having one OH group, such as 4-ethylbenzenesulfonic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, and cyclohexanol), diols (e.g., 1,2-ethanediol, 1-2-propanediol, 1,3-propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, 1,2-benzenedimethanol, catechol, and cyclohexenediol), triols (glycerol, benzenetriol, 1,2,4-butanetriol, tris(methyl alcohol)propane, tris(methyl alcohol)ethane, tris(methyl alcohol)nitropropane, trimethylolpropane, Preferably, the polymer is selected from the group consisting of glycerol or benzenetriol), tetraols (e.g., calix[4]arene, 2,2-bis(methyl alcohol)-1,3-propanediol, di(trimethylolpropane)), polyols (e.g., dipentaerythritol, 0-(+)-glucose or D-sorbitol), dihydroxy-terminated polyesters (e.g., polylactic acid), dihydroxy-terminated polyethers (e.g., poly(ethylene glycol)), acids (such as diphenylphosphinic acid), starch, lignin, monoamines (i.e., methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine), diamines (e.g., 1,4-butanediamine), triamines, diamine-terminated polyethers, diamine-terminated polyesters, monocarboxylic acids (e.g., 3,5-di-tert-butylbenzoic acid), dicarboxylic acids (e.g., maleic acid, malonic acid, succinic acid, glutaric acid or terephthalic acid, preferably maleic acid, malonic acid, succinic acid, glutaric acid), tricarboxylic acids (e.g., citric acid, 1,3,5-benzenetricarboxylic acid or 1,3,5-cyclohexanetricarboxylic acid, preferably citric acid), monothiols, dithiols, trithiols, and compounds having a mixture of hydroxyl, amine, carboxylic acid and thiol groups, such as lactic acid, glycolic acid, 3-hydroxypropionic acid, natural amino acids, unnatural amino acids, monosaccharides, disaccharides, oligosaccharides and polysaccharides (including pyranose and furanose forms), and preferably the chain transfer agent is selected from the group consisting of cyclo The hydroxybenzoates are selected from hexenedial, 1,2,4-butanetriol, tris(methyl alcohol)propane, tris(methyl alcohol)nitropropane, tris(methyl alcohol)ethane, tri(methyl alcohol)propane, tri(methyl alcohol)butane, pentaerythritol, poly(propylene glycol), glycerol, mono- and diethylene glycol, propylene glycol, 2,2-bis(methyl alcohol)-1,3-propanediol, 1,3,5-benzenetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,4-butanediamine, 1,6-hexanediol, D-sorbitol, 1-butylamine, terephthalic acid, D-(+)-glucose, 3,5-di-tert-butylbenzoic acid, and water.

[0243] In embodiments, the chain transfer agent is water, diphenylphosphinic acid, 4-ethylbenzenesulfonic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, cyclohexanol, 1,2-cyclohexanediol, 1,2-ethanediol, 1-phenyl-1,2-ethanediol, 1-2-propanediol, 1,3-propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, 1,2-benzenedimethanol, catechol, cyclohexenediol, glycerol, benzenetriol, 1,2,4-butanetriol, tris(methyl alcohol)propane, tris(methyl alcohol), The carboxylic acid may be selected from the group consisting of (methyl alcohol)ethane, tris(methyl alcohol)nitropropane, D-(+)-glucose, D-sorbitol, calix[4]arene, 2,2-bis(methyl alcohol)-1,3-propanediol, polylactic acid, poly(ethylene glycol), starch, lignin, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, 1,4-butanediamine, 3,5-di-tert-butylbenzoic acid, maleic acid, malonic acid, succinic acid, glutaric acid, terephthalic acid, citric acid, 1,3,5-benzenetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, lactic acid, glycolic acid, and 3-hydroxypropionic acid.

[0244] In embodiments, the chain transfer agent is trans 1,2-cyclohexanediol.

[0245] In an embodiment, the molar ratio of chain transfer agent to catalyst of Formula I is from 1:1 to 50:1. Preferably, the molar ratio of chain transfer agent to catalyst of Formula I is from 3:1 to 30:1. More preferably, the molar ratio of chain transfer agent to catalyst of Formula I is from 5:1 to 15:1.

[0246] In embodiments, no chain transfer agent is present.

[0247] The catalyst of formula I allows the polymerization process to be carried out at significantly lower CO2 pressures. In an embodiment, step a) is carried out at a CO2 pressure of 1 to 100 bar. Preferably, step a) is carried out at a CO2 pressure of 1 to 50 bar. More preferably, step a) is carried out at a CO2 pressure of 1 to 30 bar. Even more preferably, step a) is carried out at a CO2 pressure of 1 to 20 bar.

[0248] In a particularly preferred embodiment, step a) is carried out at a pressure of 10 to 20 bar of CO2.

[0249] In an embodiment, step a) is carried out at a pressure of CO2 between 1 and 10 bar.

[0250] In an embodiment, step a) is carried out at a temperature of 0 to 250°C. Preferably, step a) is carried out at a temperature of 0 to 150°C. More preferably, step a) is carried out at a temperature of 30 to 120°C. Most preferably, step a) is carried out at a temperature of 40 to 70°C.

[0251] In a particularly preferred embodiment, step a) is carried out at a temperature of 50°C.

[0252] In a particularly preferred embodiment, step a) is carried out at a temperature of 100°C.

[0253] In an embodiment, in step a), the compound of formula I is present in an amount of 0.0001 to 0.5 mol %, relative to the number of moles of epoxide; the epoxide is propylene oxide or cyclohexene oxide; Step a) is carried out at a CO2 pressure of 10-20 bar, Step a) is carried out at a temperature between 30 and 120°C.

[0254] In embodiments, step a) is carried out in the presence of a cyclic anhydride. In such embodiments, the resulting polycarbonate will contain a quantity of polyester. Preferably, the cyclic anhydride has a structure according to Formula II shown below: [ka] and During the ceremony, n' is 1, 2, 3, 4, 5 or 6; each Z is independently C, O, N, or S; [ka] is a double or single bond depending on the valence of Z. Preferably, n' is 1 or 2. In particular, non-limiting examples of cyclic anhydrides are: [ka] is.

[0255] The complexes of Formula I produce both excellent activity and selectivity in the ROCOP of epoxides without the need for the types of cocatalysts commonly used with monometallic salen catalysts, such as quaternary ammonium salts. Thus, in embodiments, the process is carried out in the absence of a cocatalyst.

[0256] The polymers resulting from this polymerization process are monomodal.

[0257] The polymers derived from this polymerization method have a polydispersity (

number

[0258] According to a second aspect of the present invention, there is provided a method for preparing a polyester, the method comprising: a) contacting at least one epoxide with at least one cyclic anhydride Including, A method is provided wherein step a) is carried out in the presence of a compound of formula I as defined herein.

[0259] The inventors have surprisingly discovered that compounds of formula I are also active in the ROCOP of epoxides with cyclic anhydrides to form polyesters.

[0260] Compounds according to formula I used in the second aspect of the invention may have any of the definitions listed earlier in this specification in relation to the first aspect of the invention, including all of the definitions outlined in relation to all of the subformulas and any and all specific compounds, which will not be repeated below solely for the sake of brevity.

[0261] The process of the second aspect of the present invention is the ROCOP process, in which an epoxide is copolymerized with a cyclic anhydride to form a polyester.

[0262] Cyclic anhydrides have a structure according to Formula II shown below: [ka] and During the ceremony, n' is 1, 2, 3, 4, 5 or 6; each Z is independently C, O, N, or S; [ka] is a double or single bond depending on the valence of Z. Preferably, n' is 1 or 2. In particular, non-limiting examples of cyclic anhydrides are: [ka] is.

[0263] Features of the first aspect of the invention are also features of the second aspect of the invention, including preferred and suitable definitions as needed, including the amount of compound of formula I used in step a) relative to the amount of epoxide, the definition of the epoxide used in step a), the definition and amount of chain transfer agent used in step a), and the reaction conditions (e.g., solvent, temperature) used in step a). Compounds of the Invention

[0264] According to a third aspect of the present invention, there is provided a compound having a structure according to Formula I, as defined herein.

[0265] As discussed earlier in this specification regarding the first aspect of the present invention, the compounds of formula I exhibit numerous advantages over those catalysts conventionally used in the ROCOP of epoxides in the presence of CO. The compounds are also surprisingly active in the ROCOP of epoxides to form polyesters in the presence of cyclic anhydrides.

[0266] Compounds of the invention having a structure according to Formula I can have all of the definitions outlined with respect to all of the subformulas and any and all specific compounds, as well as any of those definitions listed earlier in this specification with respect to the first aspect of the invention, which will not be repeated below solely for the sake of brevity.

[0267] The following numbered statements 1-149 are not claims, but instead describe certain aspects and embodiments of the claimed invention. 1. A method for preparing a polycarbonate, said method comprising: a) contacting carbon dioxide with at least one epoxide Including, Step a) is a compound of formula I shown below [ka] (In the formula, M1 is selected from the group consisting of Group 2 metals, Group 3 metals, transition metals, Group 13 metals, Group 14 metals and lanthanides; M 2 is selected from a Group 1 metal, a Group 2 metal, a Group 3 metal, a Group 13 metal or a lanthanide; R 1 is selected from (2-5C) alkylene, (2-5C) alkenylene and (2-5C) alkynylene, wherein 0, 1 or 2 carbon atoms in any one of said (2-5C) alkylene, (2-5C) alkenylene and (2-5C) alkynylene are replaced by a heteroatom selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene, (2-5C) alkenylene and (2-5C) alkynylene are replaced by one or more R x and optionally substituted independently by R x are halo, hydroxy, cyano, nitro, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) haloalkyl, (1-20C) alkoxy, aryl, heteroaryl, and -NR xa R xb are independently selected from R x Any of the aryl or heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-20C)alkyl, (1-20C)haloalkyl, and (1-20C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or Two or more R's located on adjacent atoms xare linked to each other so that, when taken together with the atoms to which they are attached, they form a monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-20C)alkyl, (1-20C)haloalkyl, and (1-20C)alkoxy; R 2 are each absent, hydrogen, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 2a , -C(O)-OR 2a and -C(O)-NR 2a R 2b are independently selected from R 2 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b are independently selected from hydrogen and (1-3C) alkyl; X 1 are -CH- and -CR 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4 are each independently selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl; R 4wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl and heteroaryl(1-2C)alkyl are optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy; E 1 is C and E 2 is O, S or N, or E 1 is N and E 2 is O, R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 3a , -C(O)-OR 3a , -OC(O)-R 3a , -C(O)-NR 3a R 3b , -N(R 3a )C(O)-R 3b and -NR 3a R 3b are independently selected from R 3 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; and / or Two Rs located on adjacent atoms 3are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system, any of said monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; each n is independently selected from 0, 1, 2, and 3; L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) heteroaliphatic, carbocyclyl, carbocyclyl(1-3C) alkyl, heterocyclyl, heterocyclyl(1-3C) alkyl, aryl, aryl(1-3C) alkyl, heteroaryl, heteroaryl(1-3C) alkyl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) ywhere x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2 Any of the (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, and heteroaryl(1-3C)alkyl groups may contain one or more R b where L is optionally substituted by 1 and L 2 provided that at least one of R a is independently selected from hydrogen, (1-25C)alkyl, (2-25C)alkenyl, (2-25C)alkynyl, (1-25C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, and heteroaryl(1-3C)alkyl; R a any (1-25C)alkyl, (2-25C)alkenyl, (2-25C)alkynyl, (1-25C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, or heteroaryl(1-3C)alkyl occurring therein is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; R b are each independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; G1 and G 2 is independently selected from absent and a neutral or anionic donor ligand that is a Lewis base; Q is a compound according to the structure QI or Q-II shown below: [ka] and X 2 are each independently absent or (1-3C)alkylene, said (1-3C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; X 3 are each independently absent or (1-3C)alkylene, said (1-3C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; X 4 each independently is absent or methylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; m is 1, 2, 3 or 4; R 5 are respectively hydrogen, halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 5a , -C(O)-OR 5a , -OC(O)-R 5a , -C(O)-NR 5a R 5b , -N(R 5a )C(O)-R 5b and -NR 5a R 5b are independently selected from R 5wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-3C) alkyl; and / or Two Rs located on adjacent atoms 5 are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system, any of said monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; R 6 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 6a , -C(O)-OR 6a , -OC(O)-R 6a , -C(O)-NR 6a R 6b , -N(R 6a )C(O)-R 6b and -NR 6a R 6b are independently selected from R 6 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 6aand R 6b are independently selected from hydrogen and (1-3C) alkyl; and / or Two Rs located on adjacent atoms 6 are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system, any of said monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; each p is independently selected from 0, 1, 2, or 3; R 7 are each independently selected from hydrogen or (1-3C) alkyl. A method carried out in the presence of 2. M 1 is selected from Co, Fe, Cr, Ni, Al, Ti, and Zn. 3. M 1 is selected from Co, Fe, Cr, Ni, Mg, Al, Ti, and Zn. 4. M 1 is selected from Co, Fe, Cr, Ni, Al, Zn, and Mg. 5. M 1 is selected from Co, Ni, Mg, and Zn. 6. M 1 is selected from Co, Ni, and Zn. 7. M 1 The method according to subject matter 1, wherein Co. 8. M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn. 9. M 2 is selected from Na, K, Rb and Cs. 10. M 2 is K or Na. 11. The method according to subject matter 1, wherein M1 is selected from Co, Fe, Cr, Ni, Al, Ti, Zn, and Mg, and M2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga, and Sn. 12. M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn, and M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga, and Sn. 13. M 1 is selected from Co, Mg, Fe, Cr, Ni and Zn, and M 2 is selected from Na, K, Rb and Cs. 14. M 1 is selected from Co, Fe, Cr, Ni and Zn, and M 2 is selected from Na, K, Rb and Cs. 15. M 1 is selected from Co, Mg, Ni and Zn, and M 2 is selected from Na, K, Rb and Cs. 16. M 1 is selected from Co, Ni and Zn, and M 2 is selected from Na, K, Rb and Cs. 17. M 1 is Co and M 2 is selected from Na, K, Rb and Cs. 18. M 1 and M 2 are, respectively, Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, Cr and K, Al and K, Co and Ca, Co and Sr, or Co and Ba. 19. M1 and M 2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, or Cr and K, respectively. 20. R 1 is a (2-5C) alkylene, wherein 0, 1 or 2 carbon atoms in said (2-5C) alkylene are replaced by heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is replaced by one or more R x A method according to any of the above subjects, optionally substituted independently by: 21. R x are halo, hydroxy, cyano, nitro, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) haloalkyl, (1-10C) alkoxy, aryl, heteroaryl, and -NR xa R xb are independently selected from R x Any of the aryl or heteroaryl groups in R is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms xare linked to each other so that, when taken together with the atoms to which they are attached, they form a monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-10C)alkyl, (1-10C)haloalkyl, and (1-10C)alkoxy; A method according to any of the above subjects. 22. R x are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x any of the phenyl or 5- to 6-membered heteroaryl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked together so that, when taken together with the atoms to which they are attached, they form a 5- to 7-membered monocyclic or 8- to 10-membered bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring system, any of said 5- to 7-membered monocyclic or 8- to 10-membered bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring systems optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy; A method according to any of the above subjects. 23. R xare respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, wherein any of the benzene, cyclohexane, or naphthalene groups is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; A method according to any of the above subjects. 24. M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Na, K, Rb and Cs; R 1 is a (2-5C) alkylene, and 0, 1 or 2 carbon atoms in said (2-5C) alkylene are heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is / are selected from one or more R x and optionally substituted independently by R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from Rx Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, wherein any of the benzene, cyclohexane, or naphthalene groups is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; The method of claim 1. 25. M 1 is selected from Co, Mg, Fe, Cr, Ni, Al, Ti and Zn; M 2 is selected from Na, K, Rb and Cs; R 1 is a (2-5C) alkylene, and 0, 1 or 2 carbon atoms in said (2-5C) alkylene are heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C) alkylene is / are selected from one or more R x and optionally substituted independently by R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R xAny of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene, cyclohexane, or naphthalene group, wherein any of the benzene, cyclohexane, or naphthalene groups is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; The method of claim 1. 26. R 1 has a structure according to Formula A shown below: [ka] and During the ceremony, W 1 , W 2 , W 3 , W 4 and W 5 are each independently selected from absent, —CH—, —NH—, and —O—; however, i)W 1 , W 2 , W 3 , W 4 and W 5 Three or fewer of these are not present, ii) W 1 , W 2 , W 3 , W 4 and W 5 at least two of are -CH2-; iii) -NH- is not adjacent to -O-; Provided that, -CH2-, one or two R x and any one of -NH- is optionally substituted by one R x substituted as necessary by A method according to any of the above subjects. 27. W 1 , W 2 , W 3 , W 4 and W 5 27. The method according to claim 26, wherein at least three of are -CH2-. 28. W 1 , W 2 , W 3 , W 4 and W 5 are each independently selected from absent and -CH2-, and any of -CH2- is not present in one or two R x 28. The method according to claim 26 or 27, optionally substituted by 29. R 1 but with one of the following structures: [ka] and During the ceremony, W 6 and W 7 Both are -O- or W 6 and W 7 are both -CH2-, and -CH2- is each selected from one or two R x and optionally independently substituted by W 8 is -O- or -NH-, and -NH- is R x and optionally substituted by q is 0, 1 or 2; A method according to any of the above subjects. 30.W 6 and W 7 is -CH2-, each -CH2- is one R x 30. The method according to claim 29, wherein each of the groups is independently substituted by: 31. A method according to subject matter 29 or 30, wherein q is 0 or 1, respectively. 32.M 1 is selected from Co, Fe, Cr, Ni, Al, Ti and Zn, and M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; R 1 but with one of the following structures: [ka] and During the ceremony, W 6 and W 7 Both are -O- or W 6 and W 7 are both -CH2-, and -CH2- is each selected from one or two R x and optionally independently substituted by W 8 is -O- or -NH-, and -NH- is R x and optionally substituted by R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms xare linked to each other so that, when taken together with the atom to which they are attached, they form a benzene, cyclohexane, or naphthalene group, any of said benzene, cyclohexane, or naphthalene groups being optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; each q is 0 or 1; The method of claim 1. 33. M 1 is selected from Co, Mg, Fe, Cr, Ni, Al, Ti and Zn, and M 2 is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; R 1 but with one of the following structures: [ka] and During the ceremony, W 6 and W 7 Both are -O- or W 6 and W 7 are both -CH2-, and -CH2- is each selected from one or two R x and optionally independently substituted by W 8 is -O- or -NH-, and -NH- is R x and optionally substituted by R x are respectively halo, hydroxy, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR xa R xb are independently selected from R x Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy;xa and R xb are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms x are linked to each other so that, when taken together with the atom to which they are attached, they form a benzene, cyclohexane, or naphthalene group, any of said benzene, cyclohexane, or naphthalene groups being optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; each q is 0 or 1; The method of claim 1. 34.R 1 but with one of the following structures: [ka] and During the ceremony, R y are each independently selected from hydrogen, halo, cyano, (1-4C)alkyl, (1-4C)alkoxy, (1-4C)haloalkyl, phenyl, —NH and NMe; R z is selected from hydrogen and (1-2C) alkyl; A method according to any of the above subjects. 35. R y are each independently selected from hydrogen, halo, cyano, (1-2C)alkyl, (1-2C)alkoxy, (1-2C)haloalkyl, phenyl, —NH and NMe; R z 35. The method according to claim 34, wherein is selected from hydrogen and methyl. 36. R 1 but with one of the following structures: [ka] 2. A method according to any of the above subjects, comprising: 37. M 1 and M2 are Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na or Cr and K, respectively; R 1 but with one of the following structures: [ka] 2. The method of claim 1, comprising: 38. M 1 and M 2 are respectively Zn and Na, Ni and Na, Mg and Na, Co and Na, Co and Rb, Co and Cs, Zn and Mg, Co and K, Fe and Na, Fe and K, Cr and Na, Cr and K, Al and K, Co and Ca, Co and Sr, or Co and Ba, R 1 but with one of the following structures: [ka] 2. The method of claim 1, comprising: 39. R 1 but with one of the following structures: [ka] 2. A method according to any of the above subjects, comprising: 40. R 2 are each absent, hydrogen, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, phenyl, phenyl(1-2C) alkyl, 5- to 6-membered heteroaryl, 5- to 6-membered heteroaryl(1-2C) alkyl, and —C(O)—NR 2a R 2b are independently selected from R 2wherein any of the phenyl, phenyl(1-2C)alkyl, 5- to 6-membered heteroaryl, and 5- to 6-membered heteroaryl(1-2C)alkyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b is independently selected from hydrogen and (1-3C) alkyl. 41.R 2 are absent, hydrogen, (1-3C) alkyl, (2-3C) alkenyl, (2-3C) alkynyl, phenyl, benzyl, and —C(O)—NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b is independently selected from hydrogen and (1-3C) alkyl. 42.R 2 are absent, hydrogen, (1-3C) alkyl, phenyl, benzyl, and -C(O)-NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 2a and R 2b is independently selected from hydrogen and (1-2C) alkyl. 43.R 2 are absent, hydrogen, (1-3C) alkyl, phenyl, benzyl, and -C(O)-NR 2a R 2bare independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 2a and R 2b is independently selected from hydrogen and (1-2C) alkyl. 44. R 2 are each independently selected from absent, hydrogen and (1-2C)alkyl. 45. R 2 The method according to any of the above subject matter, wherein each of is independently selected from absent or hydrogen. 46. ​​X 1 are -CH- and -CR, respectively. 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4 are each independently selected from (1-4C)alkyl, phenyl, and phenyl(1-2C)alkyl; R 4 The process according to any of the above subjects, wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy. 47. X 1 are -CH- and -CR, respectively. 4 -, -CH2-, -CHR 4 -, -CR 4 R 4 - and -PR 4 R 4 independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4The process according to any of the above subjects, wherein any phenyl in is optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy. 48. X 1 are -CH- and -CR, respectively. 4 -, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 The process according to any of the above subjects, wherein any phenyl in is optionally substituted by one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy. 49. X 1 are -CH- and -CR, respectively. 4 -, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 is each independently (1-2C) alkyl. 50. X 1 is each independently selected from -CH- or -CH2-. 51. R 2 is absent, hydrogen, (1-3C) alkyl, phenyl, benzyl and -C(O)-NR 2a R 2b are independently selected from R 2 wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 2a and R 2bare independently selected from hydrogen and (1-2C) alkyl; X 1 are -CH- and -CR, respectively. 4 -, -CH2-, -CHR 4 - and -CR 4 R 4 - are independently selected from R 4 are each independently selected from (1-2C) alkyl and phenyl; R 4 wherein any phenyl is optionally substituted by one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy. 38. The method of claim 1, 24, 32 or 37. 52. E 1 is C and E 2 is O, S or N, or E 1 is N and E 2 A method according to any of the above subjects, wherein 53. E 1 is C and E 2 A method according to any of the above subjects, wherein 54. R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 3a , -C(O)-OR 3a , -OC(O)-R 3a , -C(O)-NR 3a R 3b , -N(R 3a )C(O)-R 3b and -NR 3a R 3b are independently selected from R 3wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b is independently selected from hydrogen and (1-3C) alkyl. 55. R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryl(1-2C)alkyl, 5-6 membered heteroaryl, 5-6 membered heteroaryl(1-2C)alkyl and -NR 3a R 3b are independently selected from R 3 any of the aryl, aryl(1-2C)alkyl, 5- to 6-membered heteroaryl, and 5- to 6-membered heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R 3b is independently selected from hydrogen and (1-3C) alkyl. 56. R 3 are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and -NR 3a R 3b are independently selected from R 3 wherein any of the phenyl and 5- to 6-membered heteroaryl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 3a and R3b is independently selected from hydrogen and (1-3C) alkyl. 57. R 3 are halo, hydroxy, cyano, nitro, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, phenyl, and -NR 3a R 3b are independently selected from R 3 any phenyl in which is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 3a and R 3b is independently selected from hydrogen and (1-3C) alkyl. 58. R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3b are independently selected from R 3a and R 3b is independently selected from hydrogen and (1-3C) alkyl. 59. A method according to any of the above subjects, wherein each n is independently selected from 0, 1, 2, and 3. 60. A method according to any of the above subjects, wherein each n is independently selected from 0, 1, and 2. 61. A method according to any of the above subjects, wherein each n is independently selected from 0 and 1. 62. If n is 1, then R 3 But X 1 A method according to any of the above subjects, in a meta position. 63. A method according to any of the above subjects, wherein each n is 0. 64. R 3 are halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 3a R 3bare independently selected from R 3a and R 3b are independently selected from hydrogen and (1-3C) alkyl; each n is independently selected from 0 or 1; When n is 1, R 3 is X 1 In the meta position, 52. The method of claim 1, 24, 32, 37 or 51. 65. L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-18C) alkyl, (2-18C) alkenyl, (2-18C) alkynyl, (1-18C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, aryl(1-3C) alkyl, heteroaryl, heteroaryl(1-3C) alkyl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2Any of the (1-18C)alkyl, (2-18C)alkenyl, (2-18C)alkynyl, (1-18C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl, aryl(1-3C)alkyl, heteroaryl, and heteroaryl(1-3C)alkyl groups may contain one or more R b 10. A method according to any of the above subjects, optionally substituted by: 66. L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-15C) alkyl, (2-15C) alkenyl, (2-15C) alkynyl, (1-15C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, heteroaryl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2Any of the (1-15C) alkyl, (2-15C) alkenyl, (2-15C) alkynyl, (1-15C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl groups may contain one or more R b 10. A method according to any of the above subjects, optionally substituted by: 67. L 1 and L 2 is absent, halo, nitrate, hydroxy, (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, 5-6 membered heteroaryl, -OC(O)-R a , -OC(O)OR a , -OP(O)(R a )2, -P(O)(OR a )2, -OR a , -OS(O)2-R a (e.g., triflate), -OS(O)-(R a )2, -OS(O)-R a , -S(O)-R a , -SC(O)-R a , -SC(S)-OR a , -N(H)S(O)2-R a (e.g., triflic acid), -N-(S(O)2-R a ) 2 (e.g., triflimide), -SR a , -N(R a )-C(O)-R a , -C(O)-N(R a )2, -N(R a )2 and -O-Si(R a ) x (OR a ) y where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; 1 or L 2 Any of the (1-10C) alkyl, (2-10C) alkenyl, (2-10C) alkynyl, (1-10C) heteroaliphatic, phenyl, and 5-6 membered heteroaryl may contain one or more R b10. A method according to any of the above subjects, optionally substituted by: 68.R a is independently selected from hydrogen, (1-22C)alkyl, (2-22C)alkenyl, (2-22C)alkynyl, (1-22C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl; R a 68. The method according to any one of subjects 65-67, wherein any of the (1-22C)alkyl, (2-22C)alkenyl, (2-22C)alkynyl, (1-22C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl present therein is independently substituted with one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy. 69. R a is independently selected from hydrogen, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) heteroaliphatic, carbocyclyl, heterocyclyl, aryl, and heteroaryl; R a 68. The method according to any one of subjects 65-67, wherein any (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, heterocyclyl, aryl, or heteroaryl present therein is independently substituted with one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy. 70. R a are each independently selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)heteroaliphatic, phenyl, and 5-6 membered heteroaryl; R a68. The method according to any one of subjects 65-67, wherein any (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)heteroaliphatic, phenyl, or 5-6 membered heteroaryl present therein is independently substituted with one or more groups independently selected from halo, amino, hydroxy, (1-2C)alkyl, and (1-4C)alkoxy. 71. R b is independently substituted with one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy. 72. R b 72. The method according to any one of subjects 65-71, wherein each of 73. L 1 and L 2 but does not exist and -OC(O)-R a are independently selected from R a is (1-20C) alkyl (e.g., acetate, i.e., "OAc" or stearate) or (2-25C) alkenyl (e.g., oleate). 74. L 1 and L 2 is independently selected from absent and acetate. 75. G 1 and G 2 does not exist, or L 1 and L 2 A method according to any of the above subjects having any of such definitions appearing in subjects 65-73. 76. X 2is each independently absent or (1-2C)alkylene, said (1-2C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl. 77. X 2 is independently absent or methylene, said methylene being optionally substituted with one or two groups independently selected from (1-2C)alkyl. 78. X 2 A method according to any of the above subjects, wherein each is independently absent or methylene, said methylene being optionally substituted with one or two methyl groups. 79. X 2 The method according to any of the above subjects, wherein each is independently absent or methylene. 80. X 3 is each independently absent or (1-2C)alkylene, said (1-2C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl. 81. X 3 is independently absent or methylene, said methylene being optionally substituted with one or two groups independently selected from (1-2C)alkyl. 82. X 3 A method according to any of the above subjects, wherein each is independently absent or methylene, said methylene being optionally substituted with one or two methyl groups. 83. X 3 The method according to any of the above subjects, wherein each is independently absent or methylene. 84. X 4 A method according to any of the above subjects, wherein each is independently methylene optionally substituted with one or two methyl groups. 85. X4 The method according to any of the above subjects, wherein each is methylene. 86. A method according to any of the above subjects, wherein m is 1, 2, or 3. 87. A method according to any of the above subjects, wherein m is 2. 88. X 2 is independently absent or methylene, said methylene being optionally substituted with one or two methyl groups; X 3 are each independently absent or methylene, said methylene being optionally substituted with one or two methyl groups; X 4 are each independently methylene optionally substituted with one or two methyl groups; m is 1, 2 or 3; 65. The method of claim 1, 24, 32, 37, 51 or 64. 89. R 5 are respectively hydrogen, halo, hydroxy, cyano, nitro, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, phenyl, phenyl(1-2C)alkyl, 5-6 membered heteroaryl, 5-6 membered heteroaryl(1-2C)alkyl and -NR 5a R 5b are independently selected from R 5 wherein any of the phenyl, phenyl(1-2C)alkyl, 5- to 6-membered heteroaryl, and 5- to 6-membered heteroaryl(1-2C)alkyl is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-3C)alkyl; and / or two Rs located on adjacent atoms 5are linked to each other so that, when taken together with the atoms to which they are attached, they form benzene, a 5- to 6-membered heteroaromatic ring, a 5- to 6-membered carbocyclic ring or a 5- to 6-membered heterocyclic ring, any of said benzene, 5- to 6-membered heteroaromatic ring, 5- to 6-membered carbocyclic ring or 5- to 6-membered heterocyclic ring optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy; A method according to any of the above subjects. 90. R 5 are respectively hydrogen, halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, phenyl(1-2C) alkyl and -NR 5a R 5b are independently selected from R 5 wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-2C) alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other so that, when taken together with the atoms to which they are attached, they form benzene, a 5- to 6-membered heteroaromatic ring, a 5- to 6-membered carbocyclic ring, or a 5- to 6-membered heterocyclic ring, any of which is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; A method according to any of the above subjects. 91. R 5are respectively hydrogen, halo, hydroxy, (1-3C) alkyl, (1-3C) haloalkyl, (1-3C) alkoxy, phenyl, phenyl(1-2C) alkyl and -NR 5a R 5b are independently selected from R 5 wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 5a and R 5b are independently selected from hydrogen and (1-2C) alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene or a 5- to 6-membered heteroaromatic ring, wherein either the benzene or the 5- to 6-membered heteroaromatic ring is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; A method according to any of the above subjects. 92. R 5 are each independently selected from hydrogen and (1-2C)alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other such that, when taken together with the atoms to which they are attached, they form a benzene ring, optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; A method according to any of the above subjects. 93. R 5 are each independently selected from hydrogen and (1-2C) alkyl. 94. R 6are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R 6a , -C(O)-OR 6a , -OC(O)-R 6a , -C(O)-NR 6a R 6b , -N(R 6a )C(O)-R 6b and -NR 6a R 6b are independently selected from R 6 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; 6a and R 6b is independently selected from hydrogen and (1-3C) alkyl. 95. R 6 are halo, hydroxy, cyano, nitro, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, phenyl, and -NR 6a R 6b are independently selected from R 6 any phenyl in which is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; 6a and R 6b is independently selected from hydrogen and (1-3C) alkyl. 96. R 6 are halo, cyano, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 6a R 6bare independently selected from R 6a and R 6b is independently selected from hydrogen and (1-2C) alkyl. 97. R 6 are halo, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 6a R 6b are independently selected from R 6a and R 6b is independently selected from hydrogen and methyl. 98. R 6 is each independently selected from halo, methyl, and methoxy. 99. A method according to any of the above subjects, wherein each p is independently selected from 0, 1, or 2. 100. A method according to any of the above subjects, wherein each p is independently selected from 0 and 1. 101. R 7 are each independently selected from hydrogen or (1-2C) alkyl. 102. R 7 is each independently selected from hydrogen or methyl. 103. R 7 A method according to any of the above subjects, wherein each of 104. R 5 are each independently selected from hydrogen and (1-2C)alkyl; and / or two Rs located on adjacent atoms 5 are linked to each other such that, when taken together with the atoms to which they are attached, they form a benzene ring, optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; R 6are halo, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, and -NR 6a R 6b are independently selected from R 6a and R 6b are independently selected from hydrogen and methyl; each p is independently selected from 0 and 1; R 7 are each independently selected from hydrogen or methyl; 100. The method of claim 1, 24, 32, 37, 51, 64 or 88. 105. A method according to any of the above subjects in which Q is QI. 106. Q is one of the following structures: [ka] 2. A method according to any of the above subjects, comprising: 107. R 6 are each independently halo, methyl, and methoxy; R 7 107. The method according to claim 106, wherein each is independently hydrogen or methyl. 108. Q is a structure of: [ka] 2. A method according to any of the above subjects, comprising: 19. Q is a structure according to: [ka] 2. A method according to any of the above subjects, comprising: 110. The compound of formula I has a structure according to formula II as defined herein, wherein M 1 , M 2 , R 1 , R 2 , R 3 , R 5 , X 1 , X 2 , E 1 , E 2 , L 1, L 2 , G 1 , G 2 The method according to any of the above subjects, wherein m, n, and any moieties associated therewith have any of the definitions outlined in any of the preceding subjects. 111. The compound of formula I has a structure according to formula I-II as defined herein, wherein M 1 , M 2 , R 1 , R 2 , R 3 , L 1 , L 2 , G 1 , G 2 , Q, and any moieties associated therewith, have any of the definitions outlined in any of the preceding subjects. 112. The compound of formula I has a structure according to formulas I-III as defined herein, wherein M 1 , M 2 , X 1 , R 2 , R 3 , E 2 , L 1 , L 2 , G 1 , G 2 , n, Q, W 1 , W 2 , W 3 , W 4 , W 5 and any moieties associated therewith have any of the definitions outlined in any of the preceding subjects. 113. The compound of formula I has a structure according to formulas I-IV as defined herein, wherein M 1 , M 2 , X 1 , E 1 , E 2 , R 1 , R 2 , R 3 , L 1 , L 2 , G 1 , G 2, n, and any moieties associated therewith have any of the definitions outlined in any of the preceding subjects. 114. The compound of formula I has a structure according to formula IV as defined herein, wherein M 1 , M 2 , R 2 , R 3 , E 1 , E 2 , L 1 , L 2 , G 1 , G 2 , W 1 , W 2 , W 3 , W 4 , W 5 , n, and any moieties associated therewith have any of the definitions outlined in any of the preceding subjects. 115. The compound of formula I has a structure according to formulas I-VI as defined herein, wherein M 1 , M 2 , R 1 , R 2 , L 1 , L 2 and any moieties associated therewith have any of the definitions outlined in any of the preceding subjects. 116. The compound of formula I has a structure according to any one of the following: [ka] [ka] [ka] [ka] 2. The method of any of the above subjects, comprising: 116. A compound of formula I having a structure according to any of the following: [ka] [ka] [ka] and In the formula, L 1 and L 2 is present and has any of the definitions outlined in any of the preceding subjects, A method according to any of the above subjects. 117. L 1 and L 2 The method according to claim 116, wherein is acetate. 118. A method according to any of the above subjects, wherein in step a), the compound of formula I is present in an amount of 0.0001 to 0.5 mol %, relative to the number of moles of epoxide. 119. A method according to any of the above subjects, wherein in step a), the compound of formula I is present in an amount of 0.001 to 0.3 mol %, relative to the number of moles of epoxide. 120. A method according to any of the above subjects, wherein in step a), the compound of formula I is present in an amount of 0.01 to 0.1 mol %, relative to the number of moles of epoxide. 121. A method according to any of the above subjects, wherein in step a), the compound of formula I is present in an amount of 0.015 to 0.05 mol %, relative to the number of moles of epoxide. 122. A method according to any of the above subjects, wherein the epoxide is located on a group that is cyclic or acyclic. 123. Epoxides include cyclohexene oxide, styrene oxide, alkylene oxides (such as ethylene oxide, propylene oxide, vinyl-propylene oxide, and butylene oxide), cyclohexene oxide (limonene oxide, C 10 H 16 O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and C 11 H 22O, etc.), oxirane (oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyloxirane, 2-(2-(2-methoxyethoxy)ethoxy)methyloxirane, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyloxirane, etc.), 1,2-epoxybutane, glycidyl ether (allyl glycidyl ether, tert-butyl glycidyl ether, glycidyl methyl ether, isopropyl glycidyl ether, butyl glycidyl ether, methoxyethyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, m-tolyl glycidyl ether, glycidyl propargyl ether, beta-chloroethyl glycidyl ether, sulfur and tetrahydrofurfuryl glycidyl ether), glycidyl esters (such as glycidyl benzoate), glycidyl carbonates (such as methyl glycidyl carbonate, ethyl glycidyl carbonate and cholesteryl glycidyl carbonate), vinyl-cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 1,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide, THF-epoxides and functionalized 3,5-dioxapoxides, and mixtures of two or more thereof. 124. A process according to any of the above subjects, wherein the epoxide is selected from ethylene oxide, propylene oxide, vinyl-propylene oxide, butylene oxide, allyl glycidyl ether, tert-butyl glycidyl ether, epichlorohydrin, styrene oxide, cyclohexene oxide, vinyl-cyclohexene oxide, cyclopentene oxide, limonene oxide, and mixtures of two or more thereof. 125. A method according to any of the above subjects, wherein the epoxide is propylene oxide or cyclohexene oxide. 126. A method according to any of the above subjects, wherein the epoxide is propylene oxide. 127. A method according to any of the above subjects, wherein step a) is carried out in the presence of a chain transfer agent. 128. The method according to subject matter 127, wherein the chain transfer agent is selected from the group consisting of water, a monoalcohol, a diol, a triol, a tetraol, a polyol, a monoamine, a polyamine, a monothiol, a polythiol, a monocarboxylic acid, or a polycarboxylic acid. 129. The method according to subject matter 127 or 128, wherein the chain transfer agent is trans 1,2-cyclohexanediol. 130. The process according to subject matter 127, 128, or 129, wherein the molar ratio of chain transfer agent to catalyst of Formula I is 1:1 to 50:1. 131. The process according to subject matter 127, 128, or 129, wherein the molar ratio of chain transfer agent to catalyst of Formula I is 3:1 to 30:1. 132. A method according to any of the above subjects that does not involve the use of a chain transfer agent. 133. A method according to any of the above subjects, wherein step a) is carried out at a pressure of CO2 between 1 and 100 bar. 134. A method according to any of the above subjects, wherein step a) is carried out at a CO2 pressure of 1 to 30 bar. 135. A method according to any of the above subjects, wherein step a) is carried out at a CO2 pressure of 1 to 20 bar. 136. A method according to any of the above subjects, wherein step a) is carried out at a temperature of 0 to 250°C. 137. A method according to any of the above subjects, wherein step a) is carried out at a temperature of 0 to 150°C. 138. A method according to any of the above subjects, wherein step a) is carried out at a temperature of 40 to 70°C. 139. In step a), the compound of formula I is present in an amount of 0.001 to 0.3 mol % relative to the number of moles of epoxide; the epoxide is propylene oxide or cyclohexene oxide; Step a) is carried out at a CO2 pressure of 5 to 50 bar, Step a) is carried out at a temperature of 5 to 120°C; A method according to any of the above subjects. 140. A method according to any of the above subjects, wherein step a) is carried out in the presence of a cyclic anhydride. 141. A cyclic anhydride having a structure according to formula II shown below: [ka] and During the ceremony, n' is 1, 2, 3, 4, 5 or 6; each Z is independently C, O, N, or S; [ka] is a double or single bond depending on the valence of Z, Subject 140 methods. 142. A cyclic anhydride is: [ka] 142. The method of claim 140 or 141, wherein the method is one or more of: 143. A method for preparing a polyester, the method comprising: a) contacting at least one epoxide with at least one cyclic anhydride Including, A method wherein step a) is carried out in the presence of a compound of formula I, as defined in any one of subjects 1 to 117. 144. The method of subject 140, wherein the cyclic anhydride is as defined in any one of subjects 141 and 142. 145. The method of subject 143 or 144, wherein the epoxide is as defined in any one of subjects 122-126. 146. The method of claim 143, 144, or 145, wherein the amount of the compound of formula I used in step a) is as defined in any one of claims 118-121. 147. The process of any one of claims 143-146, wherein step a) is carried out in the presence of a chain transfer agent as defined in any one of claims 127-132. 148. The method of any one of subjects 143-147, wherein step a) is performed at a temperature defined in any one of subjects 136-138. 149. A compound having a structure according to Formula I, as defined in any one of subjects 1-117. [Example]

[0268] One or more embodiments of the invention will now be described, by way of example only, with reference to the accompanying drawings. Figure 1 shows an Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of the molecular structure of complex 1. For clarity, disorder and hydrogen atoms have been omitted, and the thermal ellipsoid is shown at 50% probability. Figure 2 shows an ORTEP diagram of the molecular structure of complex 2, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Figure 3 shows ORTEP diagrams of the molecular structures of complex 7 (top) and complex 7-(EtOH) (bottom), with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Figure 4 shows an ORTEP diagram of the molecular structure of complex 12, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Two molecules of complex 12 are shown coordinated to each other via acetate co-ligands. FIG. 5 shows an ORTEP diagram of the molecular structure of complex 10, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Figure 6 shows the polymerization data for complex 2: a) PPC molar mass (Mn: ■) and dispersity (

number

[0269] Solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Acetonitrile was obtained from a solvent purification system, degassed by several freeze-pump-thaw cycles, further dried over 3 Å molecular sieves, and stored under N. All epoxide monomers were dried over calcium hydride, fractionally distilled, degassed by bubbling with N, and stored under N. Research-grade CO was used for the polymerization studies. method General synthesis of ligand precursors

[0270] The ligand precursors shown below were synthesized according to modified literature procedures. 18 . [ka] General synthesis of catalytic compounds

[0271] The general synthesis of catalysts by diamine condensation and metal complexation was carried out in a one-pot procedure: M 2 (OAc) x (In the formula, M 2 (wherein x is Na, Mg, K, Rb, or Cs, and x is 1, 2, or 3, as appropriate) (1.03 mmol) was added to a solution of the ligand precursor (1.03 mmol) in acetonitrile (15 mL) and stirred under N2 at 25 °C for 30 min. The reaction mixture was then charged with M 1 (OAc) x (In the formula, M 1 is Co, Zn, Mg, or Ni, and x is 1, 2, or 3, as appropriate) (1.03 mmol) was added and stirred for an additional 2 hours at 25° C. Diamine (shown below) (1.03 mmol) was added dropwise to the reaction mixture and stirred at 25° C. under N for 16 hours. [ka] The resulting complex was exposed to air and oxidized by adding acetic acid (1.03 mmol) and stirred for up to 72 h (followed by 1 H NMR spectroscopy). The solution was filtered and the solvent volume reduced in vacuo. Excess acetic acid was removed by azeotropic evacuation with toluene (3 x 25 mL). The resulting solid was washed with pentane (3 x 50 mL) and dried in vacuo to give a solid.

[0272] The complexes were characterized by NMR spectroscopy, mass spectroscopy, IR spectroscopy and single crystal X-ray diffraction, and the purity was determined by elemental analysis. Characterization

[0273] 1 H NMR, solution state 13 C{ 1 For H} NMR and full 2D NMR, a Bruker Avance III HD nanobay NMR ( 1 H 400MHz, 13 A C 100 MHz NMR spectrometer was used. 13 C{ 1 For {H} NMR, a Bruker Avance III HD solid-state NMR ( 1 H 400MHz, 13 C 100MHz) was used.

[0274] MALDI-ToF analysis was performed on a Micromass MALDI micro MX spectrometer. The matrix used in combination with the complex was trans-1-[3-(4-tert-butylphenyl)-2-methyl-2-propenyldene]-malonitrile. The matrix used in combination with the polymer was dithranol.

[0275] Crystalline samples were isolated and mounted on MiTeGen MircoMounts. Crystals were cooled to 150 K using an Oxford Cryosystems nitrogen refrigerator. Data were collected using an Oxford Diffraction Supernova diffractometer using Cu Kα (λ = 1.5417 Å) radiation. The resulting raw data were processed using CrysAlisPro. The structure was solved by full-matrix least-squares refinement based on SHELXT and F2, performed in SHELXL-14, incorporated into the WinGX package.

[0276] Elemental analyses were performed by Eric Coleman of London Metropolitan University.

[0277] Gel permeation chromatography (GPC) analysis was performed using a Shimadzu LC-20AD instrument with two mixed-bed PSS SDV Linear S columns combined in series at 40 °C using THF as the eluent at a flow rate of 1 mL / min. General Procedure for Copolymerization Reactions

[0278] The catalyst and cyclohexene diol epoxide solutions (3–15 mL) were injected into a 100 mL Parr reactor equipped with a DiComp sentinel probe for in situ IR spectroscopy. The reactor was then pressurized with CO to the target reaction pressure and allowed to reach the required temperature. Example 1 Catalyst synthesis Synthesis of complex 1 [ka]

[0279] Complex 1 was synthesized by adding sodium acetate along with cobalt acetate to the ligand precursor in acetonitrile at 25°C under N2 and stirring for 30 min. This was followed by the addition of ethylenediamine at 25°C under N2 and stirring for 16 h. The resulting solution was exposed to air and then oxidized by adding an equal volume of acetic acid. The resulting suspension was filtered, and excess acetic acid was removed by azeotropic evaporation with toluene, followed by washing with pentane to yield a light brown solid.

[0280] Complex 1: (0.37 g, 0.61 mmol, 59%) [ka] HRMS (ESI / FTMS) m / z: [7-OAc] + Calculated value C 24 H 27 CoN2NaO8 553.0992; Found 553.0977. Analytical Calculated C 26 H 30 CoNaNO 10 Calculated values: C, 51.0; H, 4.9; N, 4.6%. Found values: C, 50.7; H, 4.8; N, 4.4.

[0281] Figure 1 shows an ORTEP diagram of the molecular structure of complex 1, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Synthesis of complex 2 [ka]

[0282] Complex 2 was synthesized by adding potassium acetate along with cobalt acetate to the ligand precursor in acetonitrile at 25°C under N2 and stirring for 30 min. After this, ethylenediamine was added at 25°C under N2 and stirring for 16 h. The resulting solution was exposed to air and then oxidized by adding an equal volume of acetic acid. The resulting suspension was filtered, and excess acetic acid was removed by azeotropic evaporation with toluene, followed by pentane washing to give a light brown solid.

[0283] Complex 2: (0.92 g, 1.47 mmol, 74%) 1 H NMR (400 MHz, CDCl3, 298 K) δ(ppm): 7.70 (2H, s, HC=N) 6.85 (2H, d, meta-ArH) 6.70 (2H, d, meta-ArH) 6.40 (2H, t, para-ArH) 4.31 (4H, s, CH2N=CH) 4.18-3.80 (16 H, s, O-CH2-) 1.45 (6H, s, CH3COO). 13 C{1H} NMR (125 MHz, CDCl3, 298 K) δ(ppm): 179.5 (H3CCOO) 164.8 (HC=N) 157.1 (ip-so-Ar) 152.1 (ortho-Ar) 126.1 (meta-Ar) 119.0 (ortho-Ar) 112.6 (meta-Ar) 112.4 (para-Ar) 70.2, 69.6, 66.1 (OCH2-) 59.4 (CH2-N=CH) 24.8 (H3CCOO).Molecular cation (MALDI-ToF): 510.5amu, [LCo(II)K] + . Analytical calculation value C 26 H 30 CoKN2O 10 (628.6g mol -1 );C, 49.7;H, 4.8;N, 4.5%. Measured values:C, 49.4;H, 4.7;N, 4.6%.

[0284] Figure 2 shows an ORTEP diagram of the molecular structure of complex 2, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Synthesis of complex 3 [ka]

[0285] Complex 3 was synthesized by adding rubidium acetate along with cobalt acetate to the ligand precursor in acetonitrile at 25°C under N2 and stirring for 30 min. This was followed by the addition of ethylenediamine at 25°C under N2 and stirring for 16 h. The resulting solution was exposed to air and then oxidized by adding an equal volume of acetic acid. The resulting suspension was filtered, and excess acetic acid was removed by azeotropic evaporation with toluene, followed by pentane washing to yield a light brown solid.

[0286] Complex 3: (0.38 g, 0.56 mmol, 54%) 1 H NMR (400 MHz, CDCl3, 298 K) δ(ppm): 7.70 (2H, s, HC=N) 6.86 (2H, d, meta-ArH) 6.73 (2H, d, meta-ArH) 6.42 (2H, t, para-ArH) 4.42 (4H, s, CH2N=CH) 4.19-3.84 (16 H, s, O-CH2-) 1.45 (6H, s, CH3COO). 13 C{1H} NMR (125 MHz, CDCl3, 298 K) δ(ppm): 180.1 (H3CCOO) 165.4 (HC=N) 156.4 (ip-so-Ar) 151.9 (ortho-Ar) 126.2 (meta-Ar) 118.8 (ortho-Ar) 112.8 (meta-Ar) 112.6 (para-Ar) 69.8, 69.4, 66.4 (OCH2-) 59.3 (CH2-N=CH) 24.3 (H3CCOO).Molecular cation (MALDI-ToF): 556.0amu, [LCo(II)Rb] + . Analytical calculation value C 26 H 30 CoRbNO 10 (674.9g mol -1 );C, 46.4;H, 4.5;N, 4.2%. Measured values:C, 46.3;H, 4.4;N, 4.0%. Synthesis of complex 4 [ka]

[0287] Complex 4 was synthesized by adding cesium acetate along with cobalt acetate to the ligand precursor in acetonitrile at 25°C under N2 and stirring for 30 min. This was followed by the addition of ethylenediamine at 25°C under N2 and stirring for 16 h. The resulting solution was exposed to air and then oxidized by adding an equal volume of acetic acid. The resulting suspension was filtered, and excess acetic acid was removed by azeotropic evaporation with toluene, followed by washing with pentane to give a light brown solid.

[0288] Complex 4: (0.28 g, 0.39 mmol, 51%) 1 H NMR (400 MHz, CDCl3, 298 K) δ(ppm): 7.73 (2H, s, HC=N) 6.89 (2H, d, meta-ArH) 6.74 (2H, d, meta-ArH) 6.45 (2H, t, para-ArH) 4.51 (4H, s, CH2N=CH) 4.15-3.84 (16 H, s, O-CH2-) 1.46 (6H, s, CH3COO). 13 C{1H} NMR (125 MHz, CDCl3, 298 K) δ(ppm): 179.6 (H3CCOO) 166.0 (HC=N) 155.4 (ipso-Ar) 151.2 (ortho-Ar) 126.5 (meta-Ar) 119.4 (ortho-Ar) 112.9 (meta-Ar) 112.8 (para-Ar) 69.2, 68.9, 66.5 (OCH2-) 59.9 (CH2-N=CH) 24.7 (H3CCOO).Molecular cation (MALDI-ToF): 604.4amu, [LCo(II)Cs] + . Analytical calculation value C 26 H 30 CoCsN2O 10 (722.37g mol -1 );C, 43.2;H, 4.2;N, 3.9%. Measured values: C, 43.5;H, 4.0;N, 4.0%. Synthesis of complex 5 [ka]

[0289] Complex 5 was synthesized by adding the ligand precursor and sodium acetate to methanol. A solution of ethylenediamine in methanol was added dropwise over 3 h. After the solution was cooled to room temperature, Zn(OAc)2·2(HO) was added and stirred for 1 h. The solvent was removed under reduced pressure to give the crude product as a pale yellow glassy solid. This was triturated with dichloromethane and dried under vacuum at 60 °C to give the pure product.

[0290] Complex 5: (298 mg, 0.53 mmol, 69%) 1 H NMR (400 MHz, CDCl3, 298 K) δ(ppm): 8.29 (2H, s, -HC=N-), 6.81 (4H, m, Ar-H meta ), 6.41 (2H, m, Ar-H para ), 4.22-3.60 (16H, m, -O-CH2-, =N-CH2-), 1.81 (3H, s, H3C-C(O)O). 13 C NMR (100 MHz, CDCl3, 298 K) δ(ppm): 177.0 (-C(O)O), 167.6 (-HC=N-), 150.8 (Ar-C ortho -O-CH2), 128.0 (Ar-C meta ), 120.0 (Ar-C ipso ), 117.7 (Ar-C meta ), 112.0 (Ar-C para ), 70.1 (-O-CH2-), 69.8 (-O-CH2-), 67.8 (-O-CH2-), 56.1 (=N-CH2-), 23.6 (H3C-C(O)O). Calculated value C 28 H 27 N2NaO8Zn: C, 51.49; H, 4.86; N, 5.00. Found: C, 51.80; H, 4.97; N, 5.22. Synthesis of complex 6 [ka]

[0291] Complex 6 was synthesized by adding the ligand precursor and sodium acetate to methanol. A solution of ethylenediamine in methanol was added dropwise over 3 h. After the solution was cooled to room temperature, Mg(OAc)2·4(HO) was added and stirred for 1 h. The solvent was removed under reduced pressure to give a pale yellow glassy solid as the crude product. The product was recrystallized from a methanol / diethyl ether mixture (1:10) at −20 °C. The crystals were washed with pentane, triturated with chloroform, and dried under vacuum at 40 °C to give the pure product.

[0292] Complex 6: (59.1 mg, 0.11 mmol, 15%) [ka] Synthesis of complex 7 [ka]

[0293] Complex 7 was synthesized by adding the ligand precursor and sodium acetate to methanol. A solution of 2,2-dimethylpropane-1,3-diamine in methanol was added dropwise over 3 h. After the solution was cooled to room temperature, Zn(OAc)2·2(HO) was added and stirred for 1 h. The solvent was removed under reduced pressure to give the crude product as a pale yellow glassy solid. This was triturated with ethanol and dichloromethane and dried under vacuum at 40 °C to give the pure product.

[0294] Complex 7: (343 mg, 0.57 mmol, 74%) [ka] Analytical calculation value (measured value) C 27 H 33 N2NaO8Zn: C, 53.88 (53.81); H, 5.53 (5.62); N 4.65 (4.60).

[0295] Figure 3 shows an ORTEP diagram of the molecular structure of complex 7, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Synthesis of complex 8 [ka]

[0296] Complex 8 was synthesized by adding the ligand precursor and sodium acetate to methanol. A solution of 2,2-dimethylpropane-1,3-diamine in methanol was added dropwise over 3 h. After the solution was cooled to room temperature, Ni(OAc)2·4(HO) was added and stirred for 1 h. The solvent was removed under reduced pressure to give the crude product as a pale yellow glassy solid. This was triturated with ethanol and dichloromethane and dried under vacuum at 40 °C to give the pure product.

[0297] Complex 8: (262 mg, 0.45 mmol, 58%) Synthesis of complex 9 [ka]

[0298] Complex 9 was synthesized by adding the ligand precursor and sodium acetate to methanol. A solution of 2,2-dimethylpropane-1,3-diamine in methanol was added dropwise over 3 h. After the solution was cooled to room temperature, Mg(OAc)2·4(HO) was added and stirred for 1 h. The solvent was removed under reduced pressure to give the crude product as a pale yellow glassy solid. This was triturated with ethanol and dichloromethane and dried under vacuum at 40 °C to give the pure product.

[0299] Complex 9: (179 mg, 0.32 mmol, 63%) [ka] Analytical calculation value (measured value) C 27 H 33MgN2NaO8:C, 57.82 (55.15); H, 5.93 (6.21); N 4.99 (4.40). Synthesis of complex 10 [ka]

[0300] Complex 10 was synthesized by adding the ligand precursor and sodium acetate to methanol under N2. A methanolic solution of 2,2-dimethylpropane-1,3-diamine was added dropwise over 3 h under an atmosphere of N2. After the solution was cooled to room temperature, Co(OAc)2·4(HO) (256 mg, 1.03 mmol) was added and the solution was stirred overnight. The mixture was further stirred under ambient conditions for 24 h. The solvent was removed under reduced pressure to give a dark brown glassy solid, which was dissolved in acetonitrile and diluted with diethyl ether. The precipitate was isolated by filtration and triturated once with chloroform to give the product.

[0301] Complex 10: (533 mg, 0.81 mmol, 79%) [ka] Analytical calculation value (measured value) C 27 H 33 CoN2NaO8:C, 54.46 (53.57); H, 5.59 (5.38); N 4.70 (4.73).

[0302] FIG. 5 shows an ORTEP diagram of the molecular structure of complex 10, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Synthesis of complex 11 [ka]

[0303] Complex 11 was synthesized by adding the ligand precursor and Mg(OAc)2·4(HO) to methanol. A solution of 2,2-dimethylpropane-1,3-diamine in methanol was added dropwise over 3 h. After the solution was cooled to room temperature, Zn(OAc)2·2(HO) was added and stirred for 1 h. The solvent was removed under reduced pressure to give a pale yellow glassy solid as the crude product. This was triturated with ethanol and dichloromethane and dried under vacuum at 40 °C to give the pure product.

[0304] Complex 11: (359 mg, 0.554 mmol, 72%) [ka] Analytical calculation value (measured value) C 29 H 36 MgNO 10 Zn:C, 52.59(52.48);H, 5.48(5.29);N 4.23(4.25). Synthesis of complex 12 [ka]

[0305] Complex 12 was synthesized by adding the ligand precursor and sodium acetate to methanol. A methanolic solution of o-phenylenediamine was added dropwise over 3 h. After the solution was cooled to room temperature, Zn(OAc)2·2(HO) was added and stirred for 1 h. The solvent was removed under reduced pressure, leaving a yellow-orange powder contaminated with acetic acid. The crude solid was triturated with methanol and washed with diethyl ether to remove the acid by-product, affording the desired compound.

[0306] Complex 12: (0.53 mmol, 320 mg, 68%) [ka] Analytical calculation value C 28 H 27N2NaO8Zn: C, 55.32; H, 4.48; N, 4.61. Found: C, 55.19; H, 4.62; N, 4.49.

[0307] Figure 4 shows an ORTEP diagram of the molecular structure of complex 12, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Synthesis of complex 13 [ka]

[0308] Complex 13 was synthesized by adding the ligand precursor and sodium acetate to methanol. A methanolic solution of o-phenylenediamine was added dropwise over 3 h. After the solution was cooled to room temperature, Mg(OAc)2·4(HO) was added and stirred for 1 h. The solvent was removed under reduced pressure, leaving a yellow-orange powder. The crude solid was triturated with methanol and chloroform, washed with diethyl ether, and then stirred overnight in excess ethanol. The ethanol was removed under reduced pressure to give the pure product.

[0309] Complex 13: (0.25 mmol, 144 mg, 33%) [ka] Analytical calculation value C 28 H 27 N2NaO8Mg: C, 59.33; H, 4.80; N, 4.94. Found: C, 59.14; H, 4.76; N, 4.83. Synthesis of complex 14 [ka]

[0310] Complex 14 was synthesized by adding the ligand precursor and sodium acetate to methanol under N2. A methanolic solution of o-phenylenediamine was added dropwise over 3 h under an atmosphere of N2. After the solution was cooled to room temperature, Co(OAc)2·4(HO) (256 mg, 1.03 mmol) was added and the solution was stirred overnight. The mixture was further stirred under ambient conditions for 24 h. The solvent was removed under reduced pressure to give a dark brown glassy powder. Dissolving this in acetonitrile and diluting with diethyl ether precipitated a black solid, which was removed by filtration and triturated once with chloroform to give the pure product.

[0311] Complex 14: (291 mg, 0.44 mmol, 43%) [ka] Analytical calculation value C 30 H 30 N2NaO 10 Zn:C, 54.55;H, 4.58;N, 4.24. Actual value: C, 54.35; H, 4.44; N, 4.14. HRMS(ESI / FTMS)m / z:[10-OAc] + Calculated value C 28 H 27 CoN2NaO8601.0992; Found 601.0980. Synthesis of complex 15 [ka]

[0312] Complex 15 was synthesized by adding the ligand precursor and sodium acetate to methanol. A methanol solution of 2,2-dimethylpropane-1,3-diamine was added dropwise over 3 h. The solvent was removed under reduced pressure to give a crude, pale yellow glassy solid. The resulting solid was washed with deionized water and then dissolved in MeOH. 20 equivalents of NaBH4 were added in one portion and stirred for 2 h. Water was added to quench the excess NaBH4, followed by removal of the solvent under reduced pressure. The resulting solid was washed with distilled water. The solid was then dissolved in MeOH, and Zn(OAc)2·2(H2O) and sodium acetate were added and stirred for 1 h. The solvent was removed under reduced pressure to give a crude, yellow glassy solid. This was triturated with ethanol and dichloromethane and dried under vacuum at 40 °C to give the pure product.

[0313] Complex 15: (256 mg, 0.424 mmol, 65%) [ka] Analytical calculation value (measured value) C 27 H 37 N2NaO8Zn: C, 53.52 (53.67); H, 6.15 (6.06); N 4.62 (4.68). Synthesis of complex 16 [ka]

[0314] Complex 16 was synthesized by adding the ligand precursor and sodium acetate to methanol. A solution of 2,2-dimethylpropane-1,3-diamine in methanol was added dropwise over 3 h. The solvent was removed under reduced pressure to give a crude, pale yellow glassy solid. The resulting solid was washed with deionized water and then dissolved in MeOH. 20 equivalents of NaBH4 were added in one portion and stirred for 2 h. Excess NaBH4 was quenched by adding water, followed by removal of the solvent under reduced pressure. The resulting solid was washed with distilled water. The solid was then dissolved in MeOH, and Ni(OAc)2·4(H2O) and sodium acetate were added and stirred for 1 h. The solvent was removed under reduced pressure to give a crude, yellow glassy solid. This was triturated with ethanol and dichloromethane and dried under vacuum at 40 °C to give the pure product.

[0315] Complex 16: (244 mg, 0.41 mmol, 53%) Synthesis of complex 17 [ka]

[0316] Complex 17 was synthesized under a nitrogen atmosphere. To a solution of the ligand (0.30 g, 0.769 mmol) in acetonitrile (15–40 mL) was added the appropriate KOAc (0.769 mmol), and the solution was stirred at 25 °C for 30 min. Co(OAc)2 (0.769 mmol) was then added, and the reaction mixture was stirred at 25 °C for an additional 2 h. 1,2-phenylenediamine (0.769 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. The complex was exposed to air and oxidized by adding 1 equivalent of acetic acid (44 μL, 0.769 mmol), and the solution was then cooled to room temperature to monitor the progress of the reaction. 1 The mixture was stirred for up to 72 hours while being monitored using H NMR spectroscopy. Once the oxidation was complete, the suspension was filtered and the residual solvent volume was reduced in vacuo. Excess acetic acid was removed by azeotropic distillation with toluene (3 x 50 mL). The resulting solid was washed with pentane (3 x 50 mL) and dried in vacuo to give the desired complex as a brown solid.

[0317] Complex 17 (42% yield): [ka]

[0318] FIG. 9 shows a representation of the molecular structure of complex 17, omitting disorder and hydrogen atoms for clarity. Synthesis of complex 18 [ka]

[0319] Complex 18 was synthesized under a nitrogen atmosphere. To a solution of the ligand (0.30 g, 0.769 mmol) in acetonitrile (15–40 mL) was added the appropriate KOAc (0.769 mmol), and the solution was stirred at 25 °C for 30 min. Co(OAc)2 (0.769 mmol) was then added, and the reaction mixture was stirred at 25 °C for an additional 2 h. 4,5-dichloro-o-phenylenediamine (0.769 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. The complex was exposed to air and oxidized by adding 1 equivalent of acetic acid (44 μL, 0.769 mmol), and the solution was then cooled to room temperature to monitor the progress of the reaction. 1 The mixture was stirred for up to 72 hours while being monitored using H NMR spectroscopy. Once the oxidation was complete, the suspension was filtered and the residual solvent volume was reduced in vacuo. Excess acetic acid was removed by azeotropic distillation with toluene (3 x 50 mL). The resulting solid was washed with pentane (3 x 50 mL) and dried in vacuo to give the desired complex as a brown solid.

[0320] Complex 18 (45% yield): [ka] Synthesis of complex 19 [ka]

[0321] Complex 19 was synthesized under a nitrogen atmosphere. To a solution of the ligand (0.30 g, 0.769 mmol) in acetonitrile (15–40 mL) was added the appropriate KOAc (0.769 mmol), and the solution was stirred at 25 °C for 30 min. Co(OAc) (0.769 mmol) was then added, and the reaction mixture was stirred at 25 °C for an additional 2 h. 1,2-Diamine-4,5-difluorobenzene (0.769 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. The complex was exposed to air and oxidized by adding 1 equivalent of acetic acid (44 μL, 0.769 mmol), and the solution was then cooled to room temperature to monitor the progress of the reaction. 1 The mixture was stirred for up to 72 hours while being monitored using H NMR spectroscopy. Once the oxidation was complete, the suspension was filtered and the residual solvent volume was reduced in vacuo. Excess acetic acid was removed by azeotropic distillation with toluene (3 x 50 mL). The resulting solid was washed with pentane (3 x 50 mL) and dried in vacuo to give the desired complex as a brown solid.

[0322] Complex 19 (9.1% yield): [ka] Synthesis of complex 20 [ka]

[0323] Complex 20 was synthesized under a nitrogen atmosphere. To a solution of the ligand (0.30 g, 0.769 mmol) in acetonitrile (15–40 mL) was added the appropriate KOAc (0.769 mmol), and the solution was stirred at 25 °C for 30 min. Co(OAc)2 (0.769 mmol) was then added, and the reaction mixture was stirred at 25 °C for an additional 2 h. 4,5-dimethyl-1,2-phenylenediamine (0.769 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. The complex was exposed to air and oxidized by adding 1 equivalent of acetic acid (44 μL, 0.769 mmol), and the solution was then cooled to room temperature to monitor the progress of the reaction. 1The mixture was stirred for up to 72 hours while being monitored using H NMR spectroscopy. Once the oxidation was complete, the suspension was filtered and the residual solvent volume was reduced in vacuo. Excess acetic acid was removed by azeotropic distillation with toluene (3 x 50 mL). The resulting solid was washed with pentane (3 x 50 mL) and dried in vacuo to give the desired complex as a brown solid.

[0324] Complex 20 (52% yield): [ka] Synthesis of complex 21 [ka]

[0325] Complex 21 was synthesized by adding LH2 (300 mg, 0.769 mmol), Ba(ClO4)2 (258 mg, 0.769 mmol), 4,5-dimethoxybenzene-1,2-diamine (129 mg, 0.769 mmol), and 200 mL of 1:1 MeOH:CHCl3 to a round-bottom flask and stirring for 2 h. The solvent was removed under vacuum, and the solid was dissolved in 200 mL of CHCl3. Subsequently, guanidine sulfate (1.34 g, 12.29 mmol) dissolved in 100 mL of deionized water was added to this solution and stirred overnight. The layers were separated, and the product was extracted into CHCl3, which was then dried over magnesium sulfate. The solvent was removed under reduced pressure to give a pale yellow solid (250 mg, 62% yield). A Schlenk flask was charged with the resulting solid (200 mg, 0.383 mmol), Co(OAc) (67.8 mg, 0.383 mmol), KOAc (37.6 mg, 0.383 mmol), and acetonitrile (40 mL). This was stirred for 48 h, then exposed to air, and AcOH (33 μL, 0.383 mmol) was added. The mixture was stirred for an additional 48 h and then evaporated to dryness. The solid was triturated with toluene (3 × 50 mL) and pentane (3 × 50 mL) and dried under vacuum to give a brown solid.

[0326] Complex 21 (75 mg, 29%): [ka] Synthesis of complex 22 [ka]

[0327] Complex 22 was synthesized under a nitrogen atmosphere. To a solution of the ligand (0.30 g, 0.769 mmol) in acetonitrile (15–40 mL) was added the appropriate KOAc (0.769 mmol), and the solution was stirred at 25 °C for 30 min. Co(OAc)2 (0.769 mmol) was then added, and the reaction mixture was stirred at 25 °C for an additional 2 h. (1R,2R)-(−)-1,2-diaminecyclohexane (0.769 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. The complex was exposed to air and oxidized by adding 1 equivalent of acetic acid (44 μL, 0.769 mmol), and the solution was then cooled to room temperature to monitor the progress of the reaction. 1 The mixture was stirred for up to 72 hours while being monitored using H NMR spectroscopy. Once the oxidation was complete, the suspension was filtered and the residual solvent volume was reduced in vacuo. Excess acetic acid was removed by azeotropic distillation with toluene (3 x 50 mL). The resulting solid was washed with diethyl ether (3 x 50 mL) and dried in vacuo to give the desired complex as a brown solid.

[0328] Complex 22 (68% yield): [ka] Synthesis of complex 23 [ka]

[0329] Complex 23 was synthesized by adding LH2 (1 g, 2.56 mmol), Ba(ClO4)2 (862 mg, 2.56 mmol), and 100 mL of 1:1 MeOH:CHCl3 to a round-bottom flask. A solution of ethylenediamine (171 μL, 2.56 mmol) in MeOH (5 mL) was added over 10 min, and the solution was stirred for an additional 2 h. The solvent was removed under vacuum, and the solid was dissolved in 300 mL of CHCl3. Guanidine sulfate (1.34 g, 12.29 mmol) dissolved in 200 mL of deionized water was then added to the solution and stirred overnight. The layers were separated, and the product was extracted into CHCl3, which was then dried over magnesium sulfate. The solvent was removed under reduced pressure to give a pale yellow solid (656 mg, 62% yield). The resulting solid (570 mg, 1.38 mmol) was dissolved in 400 mL of a 1:1 mixture of methanol and chloroform. NaBH (3 × 110 mg, 3 × 2.91 mmol) was added in three portions over 1 h, followed by stirring overnight. The solvent was removed under vacuum, and the resulting solid was treated with 100 mL of deionized water. The solid was then dissolved in 100 mL of dry CHCl and dried over molecular sieves. The sieves were filtered off, and the solution was evaporated to dryness. The solid was dissolved in a minimum amount (5 mL) of CHCl and precipitated with EtO (30 mL), and the solid was collected by filtration to give a pale yellow / cream product.

[0330] Complex 23: [ka] Synthesis of complex 24 [ka]

[0331] Complex 24 was synthesized by adding potassium benzoate (250 mg, 1.03 mmol) and the ligand precursor (0.40 g, 1.03 mmol) to a Schlenk flask in acetonitrile (40 mL) under a N atmosphere for 1 h. Subsequently, ethylenediamine (69 μL, 1.03 mmol) was added, and the solution was stirred overnight. Next, AlEt (175 μL, 1.08 mmol) was added, and the reaction mixture was stirred for an additional 16 h at 25 °C. Benzoic acid (131 mg, 1.08 mmol) was added, and the reaction mixture was heated at 60 °C overnight. The solid was dried in vacuo to give the target complex as a yellow solid.

[0332] Complex 24: [ka] Synthesis of complex 25 [ka]

[0333] Complex 25 was synthesized under a nitrogen atmosphere. To a solution of the ligand (0.30 g, 0.769 mmol) in acetonitrile (15–40 mL) was added the appropriate KOAc (0.769 mmol), and the solution was stirred at 25 °C for 30 min. Cr(OAc)2 (0.769 mmol) was then added, and the reaction mixture was stirred at 25 °C for an additional 2 h. Ethylenediamine (0.769 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. The complex was exposed to air and oxidized by adding 1 equivalent of acetic acid (44 μL, 0.769 mmol), and the solution was then cooled to room temperature to monitor the progress of the reaction. 1 The mixture was stirred for up to 72 hours while being monitored using H NMR spectroscopy. Once the oxidation was complete, the suspension was filtered and the residual solvent volume was reduced in vacuo. Excess acetic acid was removed by azeotropic distillation with toluene (3 x 50 mL). The resulting solid was washed with pentane (3 x 50 mL) and dried in vacuo to give the desired complex as a brown solid.

[0334] Complex 25 (33% yield). Synthesis of complex 26 [ka]

[0335] Complex 26 was synthesized under a nitrogen atmosphere. To a solution of the ligand (0.30 g, 0.769 mmol) in acetonitrile (15–40 mL) was added the appropriate KOAc (0.769 mmol), and the solution was stirred at 25 °C for 30 min. Next, Fe(OAc)2 (0.769 mmol) was added, and the reaction mixture was stirred at 25 °C for an additional 2 h. Ethylenediamine (0.769 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. The complex was exposed to air and oxidized by adding 1 equivalent of acetic acid (44 μL, 0.769 mmol), and the solution was then heated to 1000°C for 1 h. 1 The mixture was stirred for up to 72 hours while being monitored using H NMR spectroscopy. Once the oxidation was complete, the suspension was filtered and the residual solvent volume was reduced in vacuo. Excess acetic acid was removed by azeotropic distillation with toluene (3 x 50 mL). The resulting solid was washed with pentane (3 x 50 mL) and dried in vacuo to give the desired complex as a brown solid. Synthesis of complex 27 [ka]

[0336] Complex 27 was synthesized under a N2 atmosphere. The appropriate metal acetate salt ([M(OAc)n] (where M = Na, K, Rb, Cs, Ca, Sr, or Ba) (1.03 mmol) was added to a solution of the ligand precursor (0.40 g, 1.03 mmol) in acetonitrile (15 mL), and the solution was stirred at 25 °C for 30 min. Co(OAc)2 (0.18 g, 1.03 mmol) was then added, and the reaction mixture was stirred at 25 °C for an additional 2 h. Ethylenediamine (69 μL, 1.03 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. Acetic acid was removed by azeotropic distillation with toluene (3 × 25 mL). The resulting solid was washed with pentane (3 × 50 mL) and dried in vacuo to give the desired complex as a brown solid.

[0337] Complex 27: (0.55 g, 0.88 mmol, 86%)

[0338] FIG. 10 shows the infrared spectrum of complex 27. Synthesis of complex 28 [ka]

[0339] Complex 28 was synthesized under a N2 atmosphere. The appropriate metal acetate salt ([M(OAc)n] (where M = Na, K, Rb, Cs, Ca, Sr, or Ba) (1.03 mmol) was added to a solution of the ligand precursor (0.40 g, 1.03 mmol) in acetonitrile (15 mL), and the solution was stirred at 25 °C for 30 min. Co(OAc)2 (0.18 g, 1.03 mmol) was then added, and the reaction mixture was stirred at 25 °C for an additional 2 h. Ethylenediamine (69 μL, 1.03 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. Acetic acid was removed by azeotropic distillation with toluene (3 × 25 mL). The resulting solid was washed with pentane (3 × 50 mL) and dried in vacuo to give the desired complex as a brown solid.

[0340] Complex 28: (0.68 g, 0.91 mmol, 89%)

[0341] FIG. 11 shows the infrared spectrum of complex 28. Synthesis of complex 29 [ka]

[0342] Complex 29 was synthesized under a N2 atmosphere. The appropriate metal acetate salt ([M(OAc)n] (where M = Na, K, Rb, Cs, Ca, Sr, or Ba) (1.03 mmol) was added to a solution of the ligand precursor (0.40 g, 1.03 mmol) in acetonitrile (15 mL), and the solution was stirred at 25 °C for 30 min. Co(OAc)2 (0.18 g, 1.03 mmol) was then added, and the reaction mixture was stirred at 25 °C for an additional 2 h. Ethylenediamine (69 μL, 1.03 mmol) was added dropwise to the reaction mixture, which was stirred at 25 °C for 16 h. Acetic acid was removed by azeotropic distillation with toluene (3 × 25 mL). The resulting solid was washed with pentane (3 × 50 mL) and dried in vacuo to give the desired complex as a brown solid.

[0343] Complex 29: (0.63 g, 0.88 mmol, 86%): Analytical calcd. C 26 H 30 BaCoN2O 10 (726.8g mol -1 ): C, 43.0; H, 4.2; N, 3.9%. Measured values: C, 43.1; H, 4.4; N, 3.9%.

[0344] FIG. 12 shows the infrared spectrum of complex 29. Synthesis of complex 30 [ka]

[0345] Complex 30 was synthesized by combining the dialdehyde ligand precursor (1.02 mmol), Co(OAc)2 (1.02 mmol), and Ca(OAc)2 (1.02 mmol) in dry acetonitrile (15 mL) under a nitrogen atmosphere to form a yellow-orange suspension, which was stirred at room temperature for 30 minutes. Ethylenediamine (1.02 mmol) was added to the suspension, immediately resulting in a dark reddish-brown solution. After stirring the solution overnight at room temperature under a nitrogen atmosphere, acetic acid (2.04 mmol) was added, and the reaction was stirred open to air for 3 days. The solution was filtered to remove insoluble, unreacted Co(II) species, and the brown solution was evaporated in vacuo to give a dark brown solid. The solid was azeotropically washed with toluene (3 × 50 mL) to remove residual acetic acid and with hexane (3 × 50 mL) to remove residual toluene. The solid was then dried in vacuo overnight.

[0346] Complex 30 (56% yield): (0.39 g, 0.57 mmol, 56%) [ka]

[0347] FIG. 13 shows an ORTEP diagram of the molecular structure of complex 30, with disorder and hydrogen atoms omitted for clarity, and thermal ellipsoids shown at 50% probability. Complex 31 [ka]

[0348] Complex 31 was synthesized by combining the dialdehyde ligand precursor (1.02 mmol), Co(OAc)2 (1.02 mmol), and Sr(OAc)2 (1.02 mmol) in dry acetonitrile (15 mL) to form a yellow-orange suspension, which was stirred for 30 minutes at room temperature under a nitrogen atmosphere. Ethylenediamine (1.02 mmol) was added to the suspension, immediately resulting in a dark red-brown solution. After stirring the solution overnight at room temperature under a nitrogen atmosphere, acetic acid (2.04 mmol) was added, and the reaction was stirred open to air for 3 days. The solution was filtered to remove insoluble, unreacted Co(II) species, and the brown solution was evaporated in vacuo to give a dark brown solid. The solid was azeotropically washed with toluene (3 × 50 mL) to remove residual acetic acid and with hexane (3 × 50 mL) to remove residual toluene. The solid was then dried in vacuo overnight.

[0349] Complex 31 (40% yield): (0.30 g, 0.41 mmol, 40%) [ka] Complex 32 [ka]

[0350] Complex 32 was synthesized by combining the dialdehyde ligand precursor (1.02 mmol), Co(OAc)2 (1.02 mmol), and Ba(OAc)2 (1.02 mmol) in dry acetonitrile (15 mL) to form a yellow-orange suspension, which was stirred for 30 minutes at room temperature under a nitrogen atmosphere. Ethylenediamine (1.02 mmol) was added to the suspension, immediately resulting in a dark red-brown solution. After stirring the solution overnight at room temperature under a nitrogen atmosphere, acetic acid (2.04 mmol) was added, and the reaction was stirred open to air for 3 days. The solution was filtered to remove insoluble, unreacted Co(II) species, and the brown solution was evaporated in vacuo to give a dark brown solid. The solid was azeotropically washed with toluene (3 × 50 mL) to remove residual acetic acid and with hexane (3 × 50 mL) to remove residual toluene. The solid was then dried in vacuo overnight.

[0351] Complex 32 (21% yield): (0.17 g, 0.22 mmol, 21%) [ka] Example 2 Characterization 1 H NMR spectroscopy

[0352] Successful metalation of the ligand precursor is 1 This was observed by H NMR spectroscopy (CDCl3, 298 K) by observing the reduction of the phenolic oxygen peak at 10.86 ppm and the addition of acetate proton resonances at 0.80–2.00 ppm. Furthermore, a significant upfield shift was observed when comparing the aldehyde in the ligand precursor with the imine (optional) in the catalyst. Two metal precursors could be added together, selectively forming complexes 1–4 due to the difference in the size of the metals (Co(II); 0.75 Å, Na(I); 1.10 Å, K(I); 1.50 Å, Rb(I); 1.60 Å, and Cs(I); 1.70 Å) and the coordination environment in each of the binding cavities (NO2; 1.9 Å, 18-C-6; 2.7 Å).

[0353] Complexes 7–11 are typically highly fluxional in solution (CDCl3, C2D2Cl4) at room temperature, facilitated by the flexible C3 diimine backbone. Variable-temperature NMR spectroscopy (328–398 K) enabled the characterization of these complexes in the rapid exchange phenomenon. Complex 10, which differs in having two acetate co-ligands capping each face of the macrocyclic framework, yields a well-defined NMR spectrum at room temperature, implying a more rigid ligand conformation reinforced by such a saturated coordination environment, consistent with the observed solid-state structure (Figure 5). On the other hand, complex 1 exhibits two different acetate binding modes, but only one in NMR, indicating rapid exchange between the two different binding modes. Complexes 12, 13, and 14 all exhibit very low solubility between 298–398 K, as confirmed by CP-MAS solid-state NMR spectroscopy. 13 C NMR characterization was required. 1 Observation of one imine and three crown ether environments by H NMR spectroscopy reveals that C 2h This indicates time-averaged molecular symmetry. However, complexes 6, 11, 13, and 15 all show additional splitting of the crown-methylene resonances. This desymmetrization of the complexes is likely caused by increased rigidity of the crown moiety, but the presence of asymmetric metals attached to the macrocycle cannot be ruled out. All complexes appear to be monomeric in solution and under the reaction conditions. 2D DOSY NMR spectroscopy

[0354] 2D DOSY NMR experiments (CDCl3, 298 K) yielded single diffusion coefficients for each of complexes 1–4, indicating that they are single species in solution. Using the Stokes-Einstein equation (a viscosity of chloroform of 0.54 mPa·s), we calculated approximate hydrodynamic radii of 5.14 Å, 5.17 Å, 5.65 Å, and 6.66 Å for complexes 1–4, respectively. These hydrodynamic radii in solution are in good agreement with the solid-state hydrodynamic radii calculated for complexes 1 and 2, indicating that they are monomeric complexes in both the solid and solution states. On the other hand, complexes 3 and 4 have smaller hydrodynamic radii in solution than the calculated solid-state radii, suggesting that the nuclei are monomeric in solution but dimeric / multimeric in the solid state. This has been observed previously for other complexes incorporating 18-crown-6 moieties and is rationalized by the large ionic radii of Rb and Cs, which favor higher coordination numbers leading to multimeric species. MALDI-ToF mass spectrum

[0355] MALDI-ToF mass spectra show the molecular cation, [ligand precursor-Co(II)M] for complexes 1, 2, and 4, respectively. 2 The peaks at 495 m / z, 511 m / z, and 604 m / z correspond to the isotope distribution patterns calculated for the molecular formulae of complexes 1–4. Paramagnetic study

[0356] Both Ni(II) complexes 8 and 16 were observed to be paramagnetic, with μ = 2.47 BM and 2.57 BM, respectively. Attempts to characterize the complexes by X-band electron paramagnetic resonance (EPR) spectroscopy were unsuccessful. The EPR silence of the Ni(II) complexes is due to the large zero-field splitting, making it impossible to observe the active transition.

[0357] A highly concentrated sample of the Ni complex (10 mM, toluene) produced a weak resonance at g = 1.999 by comparison with a 2.7 mM Cu(II) standard (Cu-tetraphenylporphyrin), but the approximate concentration of this weak component was determined to be <1 nM. This is proposed to be due to a Ni(II) / Ni(III) equilibrium with spin density localized at the phenolate moiety, as previously observed in paramagnetic phenolate complexes. Crystallographic studies

[0358] The structures of the prepared complexes could in some cases be confirmed by X-ray crystallography: Complexes 1 and 2

[0359] Crystals suitable for single crystal X-ray diffraction were obtained by vapor diffusion of pentane (complex 1) or diethyl ether (complex 2) into saturated solutions of the complexes in dichloromethane and are shown in Figures 1 and 2, respectively. Structural elucidation confirmed the formation of the desired heterodinuclear complexes. Complexes 1 and 2 were shown to be isomorphous and both are monomers in the solid state, with O h The cobalt center occupies the imine-phenol cavity, and the Group 1 metal occupies the crown-ether moiety. This is consistent with the larger van der Waals radius of potassium compared to sodium. 2 Distance (M 2 The axial angles (Na = 3.388 Å, K = 3.698 Å, Rb = 3.877 Å) are measurably increased. One of the acetates is shown to bridge between the cobalt and alkali metal centers, while the other acetate terminates at the cobalt. The structures of complexes 1 and 2 suggest the formation of a cobalt "ate" species. Complexes 7, 10, 12 and 15

[0360] Single crystals suitable for X-ray diffraction of complexes 7, 10, 12, and 15 were obtained by slow evaporation of CHCl3 solutions. Crystals of complex 7-(EtOH) were obtained by slow evaporation of an ethanol solution, and crystals of complex 10 were obtained by slow diffusion of pentane into dichloromethane. Complexes 7, 7-(EtOH), and 10 are monomeric in the solid state, while complex 12 is observed to be a dimer with an acetate ion bridge. As evidenced by the asymmetric C-O bond distances of the coligands and the short MO distances toward the metal in the salen moiety, all of the complexes form "ate" complexes with the oxygen of the acetate anion localized at the transition metal. This is most strikingly exemplified in complex 7-(EtOH), which shows that the acetate is bound to zinc in parallel with one ethanol molecule bound to the sodium ion. The formation of the "ate" complex allows the retention of the Lewis acidic sodium ion, favoring epoxide coordination. Interestingly, complex 10 shows two acetates bridging between cobalt and sodium, while complex 1 has one bridging acetate and one monodentate acetate. Complex 15, with its highly asymmetric binding of sodium to the crown ether moiety, forms an intramolecularly linked coordination polymer with bridging acetate co-ligands, either causing or resulting in large distortions of the solid-state structure. In the context of these data, complexes 7 and 15 have similar C3 N,N'-backbones, but the C1 molecular symmetry of complex 15 (inferred from NMR spectroscopy) and the highly deformable structure observed in the case of complex 7 are quite different. 1 C estimated from H NMR 2h Symmetry can be contrasted with symmetry. Example 3 Polymerization study

[0361] The synthesized complexes were explored as catalysts for the copolymerization of various epoxide monomers, including PO and CHO: Propylene oxide

[0362] Complexes 1-4 were tested in a CO2 / PO2 ROCOP at 50 °C using 3.5 mM catalyst, neat PO2 (6 mL, 14 M), and 20 bar CO2 pressure. 1 1 H NMR was used to calculate by comparison of the methine protons to PO (4.92 ppm) to an internal standard (10 equivalents of mesitylene).

[0363] The polymerization results are shown in Table 1 below: [Table 1] a Reaction conditions: catalyst (0.025 mol%), PO (6 mL, 14 M), 1,2-cyclohexenediol (0.5 mol%, 70 mM), 20 bar CO , 50 °C, except for entries 3, 4, and 5 (which used 0.25 mol%, 0.125 mol%, and 0 mol% 1,2-cyclohexenediol, respectively). b The PO conversion is expressed as a percentage of the theoretical maximum (100%); by comparison of the relative integrals of the resonances assigned to polycarbonate (4.92 ppm), cyclic carbonate (4.77 ppm), and polyether (3.46-3.64 ppm) relative to the internal standard mesitylene (6.70 ppm, 10 equivalents). 1 It was determined from the H NMR spectrum. c Expressed as a percentage of the theoretical maximum (100%) of CO2 uptake; polyether (3.46-3.64 ppm) versus polycarbonate (4.92 ppm) and cyclic carbonate (4.77 ppm) 1 The relative integrals of the 1 H NMR resonances were compared. d Expressed as a percentage of the amount of polymer formed relative to the theoretical maximum (100%); for cyclic carbonate (4.77 ppm) versus polycarbonate (4.92 ppm) 1 The relative integrals of the 1 H NMR resonances were compared. e Turnover number (TON) = moles of PO consumed / moles of catalyst. f Turnover frequency (TOF) = TON / hour (hours). g k p =k obs / [catalyst] 1 ;ln[PO] t k calculated as the slope of a semi-logarithmic plot of / [PO] versus time obs . h M n The solubility was determined by GPC in THF, calibrated using narrow polystyrene standards. i Catalyst (0.025 mol%, 3.5 mM), PO (6 mL, 14 M), 1,2-cyclohexanediol (0.5 mol%, 70 mM), 30 bar CO2, 70 °C. J Catalyst (0.025 mol%, 3.5 mM), PO (3 mL, 7 M), diethyl carbonate (3 mL), 1,2-cyclohexanediol (0.5 mol%, 70 mM), 20 bar CO2, 50 °C. K Catalyst (0.05mol%, 7.1mM), PO (14mL, 14M), KI (0.05mol%, 7.1mM), 15bar CO2, 25°C. L Catalyst (0.2 mol%, 10.0 mM), PO (0.5 mL, 4.6 M), toluene / chloroform (1 mL), PPNX (0.2 mol%, 10.0 mM), H2O (2.0 mol%, 1 M), 15 bar CO2, 25 °C. M Catalyst (0.05 mol%, 7.2 mM), PO (1 mL, 7 M), 1,2-dimethoxyethane (1 mL), methanol (1.0 mol%, 0.14 M), 14 bar CO2, 25 °C. N Catalyst (0.001 mol%, 1.7 μM), PO (12 mL, 14 M), adipic acid (0.4 mol%, 0.68 M), 25 bar CO2, 75 °C. OCatalyst (7.5 mol%, 0.25 M, 1 mL (1 M THF solution)), tributylammonium carbonate (TBAC) (2.5 mol%, 0.09 M), PO (2 mL, 7 M), THF (1 mL), 10 bar CO, 40 °C. P Catalyst (50 mg), PO (100 mL, 14 M), sebacic acid (95 mmol, 0.95 M), 40 bar CO2, 50 °C.

[0364] Table 1 shows that the catalysts of the present invention (entries 1-9, Table 1), especially complex 2, exhibit excellent catalytic performance with very high CO uptake in terms of activity, selectivity, and yield for PPC polyols. Furthermore, the data highlight that the catalysts of the present invention are capable of preparing low molar mass polycarbonate polyols with high efficiency without requiring impractically high acid loadings.

[0365] By utilizing the data obtained from catalyst loading experiments, the molar mass (kg mol -1 A plot of the % % copolymerization versus turnover number (TON) can be obtained (Figure 6a). The narrow monomodal dispersity indicates that the polymerization was well controlled.

number

[0366] A major drawback to conventional salen:cocatalyst combinations for ROCOP catalysis is the complexity of the resulting rate laws. They are often reported to have catalytic order dependence between 1 and 2, cocatalyst dependence between 0.5 and 2, linear dependence on epoxide concentration, and zero-order dependence on CO pressure. The complexity of the rate laws leads to a lack of understanding of the role of the cocatalyst, whether it solely provides the attacking nucleophile for ring-opening, stabilizes the metal-containing salen species and provides the attacking nucleophile, or is a combination, as its role also appears to depend on both the ratio and concentration of cocatalyst to catalyst. A thorough understanding of the rate laws demonstrating the polymerization method of the present invention will facilitate future industrial optimization and scale-up.

[0367] To determine the order of dependence of epoxide concentration, 3.57 mM of complex 2 was dissolved in a 50:50 mixture of PO:diethyl carbonate (6 mL total volume) to give a resulting PO concentration of 7 M and heated to 50 °C. A sigmoidal feature in the conversion time plot was observed, which may correspond to poor initiation under dilution. The epoxide concentration vs. time (ln([PO])) from 30 to 90% epoxide conversion was t A semi-logarithmic plot of (k / [PO]) versus (t) reveals a linear relationship (k obs =3.82×10 -5 s -1 , R 2 = 0.9992) was shown (Figure 7a).

[0368] To determine the order of dependence of catalyst concentration, a series of PO / CO2ROCOP reactions were carried out using a range of complex 2 concentrations (1.56–7.13 mM) in neat PO (14 M), 20 bar CO2, and 50 °C. All polymerization reactions gave perfectly alternating PPCs, with no ether linkages or significant cyclic carbonate (<5%) by-products. 1 It was not observed by H NMR spectroscopy. A linear relationship (ln(k obs) versus ln([cat])) with a slope of 0.96 (R 2 = 0.9526), ​​indicating a linear dependence on catalyst concentration (Fig. 7b).

[0369] The dependence on CO2 pressure was observed over the CO2 pressure range from 5 to 30 bar using 3.57 mM catalyst and neat PO (14 M) at 50 °C. obs ) was determined by measuring the observed rate constant (k obs vs. P CO2 ) showed a near-zero-order dependence on CO2 pressure between 10 and 25 bar. A rate decrease was observed at pressures <10 bar, attributed to increased cyclic carbonate formation. At CO2 pressures >20 bar, a decrease in activity was observed, consistent with previous observations, which may be due to increased CO2 gas, which reduces the total catalyst and epoxide concentrations (Figure 7c). Speed=[Cat] 1 [PO] 1 [CO2] 0

[0370] Overall, the reaction operates with near-second-order kinetics: first order in both catalyst and epoxide concentration, and near-zero order in CO pressure. This is consistent with previously reported binuclear systems for CO / CHO copolymerization and with the simple kinetics obtained using quaternary ammonium salt-tethered salen.

[0371] Certain complexes were tested in a CO2 / PO2 ROCOP, and the polymerization results are shown in Tables 1a-1d below: [Table 1a] a Reaction conditions: catalyst (0.025 mol%, 3.5 mM), PO (6 mL, 14 M), 1,2-cyclohexanediol (0.5 mol%, 70 mM), 20 bar CO2, 50 °C. [Table 1b] [Table 1c] a Reaction conditions: catalyst (0.025 mol%, 3.5 mM), PO (6 mL, 14 M), 1,2-cyclohexanediol (0.5 mol%, 70 mM), 20 bar CO2, 50 °C. [Table 1d] a Reaction conditions: catalyst (0.025 mol%, 3.5 mM), CHO (6 mL, 9.9 M), 1,2-cyclohexanediol (0.5 mol%, 70 mM), 20 bar CO2, 50 °C.

[0372] A temperature dependence study of the rate and selectivity of PO / CO2ROCOP using complex 2 was also attempted over the temperature range of 40-70 °C. Polymerizations were carried out under high CO2 pressure (20 bar), with a catalyst loading of 3.57 mM, and neat PO (14 M). The polymerization results are shown in Table 2 below: [Table 2] a Reaction conditions: catalyst (0.025 mol%), PO (6 mL, 14 M), CTA (20 equiv.), 20 bar CO2. b The PO conversion is expressed as a percentage of the theoretical maximum (100%); by comparison of the relative integrals of the resonances assigned to polycarbonate (4.92 ppm), cyclic carbonate (4.77 ppm), and polyether (3.46-3.64 ppm) relative to the internal standard mesitylene (6.70 ppm, 10 equivalents). 1 It was determined from the H NMR spectrum. c Expressed as a percentage of the theoretical maximum (100%) of CO2 uptake; polyether (3.46-3.64 ppm) versus polycarbonate (4.92 ppm) and cyclic carbonate (4.77 ppm) 1 The relative integrals of the 1 H NMR resonances were compared. dExpressed as a percentage of the amount of polymer formed relative to the theoretical maximum (100%); for cyclic carbonate (4.77 ppm) versus polycarbonate (4.92 ppm) 1 The relative integrals of the 1 H NMR resonances were compared. e Turnover number (TON) = moles of PO consumed / moles of catalyst. f Turnover frequency (TOF) = TON / hour (hours). g k p =k obs / [catalyst] 1 ;ln[PO] t k calculated as the slope of a semi-logarithmic plot of / [PO] versus time obs . h M n The solubility was determined by GPC in THF, calibrated using narrow polystyrene standards. * 30 bar CO2

[0373] All polymerizations are 1 It showed excellent CO2 uptake (>99%) with trace amounts of polyether linkages as observed by H NMR spectroscopy. -1 From 834h -1 An increase in activity of up to 90% was observed at 70 °C and 20 bar CO2, respectively. At 70 °C and 20 bar CO2, a decrease in polymer selectivity from 93% to 63% was observed, with a concomitant increase in PC. Even when the reaction was carried out at a higher CO2 pressure (30 bar), no cyclic carbonate formation was observed, and polymer selectivity of >90% was restored. Furthermore, all polymerizations showed well-defined monomodal polymer distributions.

number

[0374] The synthesized complexes were also investigated as catalysts for the ROCOP of CO2 / CHO. Polymerizations were typically carried out at 1 bar CO2 pressure and 100°C using 10 equivalents of trans-1,2-cyclohexanediol as a chain transfer agent (CTA), producing low molecular weight polyols. To avoid high viscosity events, the catalyst loading of the higher rate complexes was varied. The polymerization results are shown in Table 3 below: [Table 3] a Selectivity of PCHC over trans-cyclohexene carbonate (no ethers observed). Selectivity of cyclic carbonate (δ 4.00 ppm) and ether linkage (δ 3.45 ppm) over PCHC (δ 4.65 ppm). 1 Determined by integration of 1 H NMR resonances. b 1 Cyclohexene oxide consumed as a percentage of total starting amount, determined by 1 H NMR spectroscopy. c Turnover number (TON) = moles of CHO consumed / moles of catalyst. The moles of CHO consumed are the same as those of cyclic carbonate (δ 4.00 ppm) and PCHC (δ 4.65 ppm). 1 It was determined by dividing the sum of the integrals of the H NMR resonances by the sum of CHO (δ 3.05 ppm), cyclic carbonate (δ 4.00 ppm) and PCHC (δ 4.65 ppm) and multiplying by the initial number of moles of CHO. d Turnover frequency (TOF) = TON / hour. e In THF, narrow M n Determined by SEC calibrated against polystyrene standards; polydispersity is shown in brackets. f 0.1 mol% catalyst loading; g 0.02 mol% catalyst loading, 1:10:4000. h 0.004 mol% catalyst loading, 1:10:25000, 120°C, 20 bar CO2. i 0.02mol% catalyst loading j Catalysis conditions: catalyst: CHD:CHO 1:10:1000, 1 bar CO2 pressure, and in epoxide without solvent.

[0375] The turnover frequency (TOF) is 4 digits (0-1590h) at 1 bar CO2 pressure. -1 ), while the selectivity for polycyclohexene carbonate (PCHC) formation ranges from 43 to >99%. Generally, the onset of trans-cyclic carbonate formation is significantly higher, above 100 °C, but this barrier is much lower for selected catalysts. For all magnesium catalysts, lower TOF (0-7 h) was observed. -1 ) and lower selectivities for PCHC formation (43–73%) were observed, the latter being driven by competing trans-cyclic carbonate formation (Table 3, entries 5–7). The zinc catalyst was moderately active (12–33 h -1 ), for complex 7, 1 No by-products were detectable by H NMR spectroscopy. Across the zinc series, the more flexible C3 backbone in complex 7 appears to slow the polymerization rate (Table 3, entries 1–3), while the use of complex 15 with a different diamine resulted in a slight increase in activity with a concomitant decrease in selectivity (Table 3, entries 1 and 4).

[0376] Significant improvements were observed in the case of the nickel analogue, with complex 16 achieving 98% selectivity for up to 103 h. -1 (Table 3, entries 9 and 10). However, for the cobalt series, the observed change in polymerization rate was most pronounced (Table 3, entries 11, 13, and 14), with a rate acceleration of over 30-fold observed upon replacing the aliphatic C3 and C2 backbones. For complex 1, the TOF was 1590 h -1A TOF of 4343 h was recorded, making this the most active and highly selective catalyst reported to date for ROCOP of CHO / CO2 at 1 bar CO2. Increasing the polymerization temperature to 120 °C accelerated the formation of trans-cyclic carbonate. Increasing the CO2 pressure to 20 bar in a stainless steel reactor with improved stirring yielded a TOF of 4343 h at 120 °C. -1 This enabled an improvement in TOF (Table 3, entry 13).

[0377] Given the excellent activity of complex 1, the polymerization kinetics was investigated by in-situ FTIR spectroscopy in dilute solution in diethyl carbonate. obs Near-first-order kinetics with respect to the catalyst were observed, as can be seen from a linear-log plot of the catalyst concentration versus the catalyst concentration (Figures 8c and 8d). This is qualitatively supported by the very high TOF attainable at very low catalyst loadings ([CHO]:[catalyst] = 1:25,000, Table 3, entry 13). The order of the epoxide was determined by a log plot of the concentration over time from 5 to 70% conversion (Figure 8a). The data show a linear decline in ln([CHO] / [CHO]), indicating a first-order dependence on [CHO]. No statistically significant correlation was observed between CO2 pressure and rate, demonstrating a zero-order dependence on the gas (Figure 8b). Other Epoxide Monomers

[0378] Complex 2 was tested in ROCOP with CO and a series of acyclic and cyclic epoxide monomers. The polymerization results are shown in Table 4 below: [Table 4] a Reaction conditions: catalyst (3.57 mM), neat epoxide (6 mL), CTA (20 equiv), 20 bar CO2, 50 °C. bThe PO conversion is expressed as a percentage of the theoretical maximum (100%); calculated by comparing the relative integrals of the resonances assigned to polycarbonate (4.81 ppm, 1H), cyclic carbonate (4.38 ppm, 1H), and polyether (3.30-3.55 ppm, 3H) with the internal standard mesitylene (6.59 ppm, 10 equivalents (30H)). 1 It was determined from the H NMR spectrum. c Expressed as a percentage of the theoretical maximum (100%) of CO2 uptake; polyether (3.30-3.55 ppm, 3H) versus polycarbonate (4.81 ppm, 1H) and cyclic carbonate (4.38 ppm, 1H). 1 The relative integrals of the 1 H NMR resonances were compared. d Expressed as a percentage of the amount of polymer formed relative to the theoretical maximum (100%); for cyclic carbonate (4.38 ppm, 1H) versus polycarbonate (4.81 ppm, 1H) 1 The relative integrals of the 1 H NMR resonances were compared. e Turnover number (TON) = moles of PO consumed / moles of catalyst. f Turnover frequency (TOF) = TON / hour (hours). g k p =k obs / [catalyst] 1 ;k obs is ln[PO] t Calculated as the slope of a semi-logarithmic plot of / [PO] versus time. [Catalyst] = 3.57 mM. h M n The solubility was determined by GPC in THF, calibrated using narrow polystyrene standards. PO = propylene oxide, vPO = vinyl propylene oxide, AGE = allyl glycidyl ether, t BGE = tert-butyl glycidyl ether, CHO = cyclohexene oxide, vCHO = vinylcyclohexene oxide, CPO = cyclopentene oxide.

[0379] Overall, the catalyst:1 Excellent CO selectivity (>99%) was observed with no polyether linkages as observed by H NMR spectroscopy. Excellent polycarbonate selectivity (>95%) was observed with traces of cyclic carbonates (<5%), excluding styrene oxide (SO).

[0380] In general, the cyclic epoxides proceeded with higher rate constants compared to the acyclic examples. Furthermore, the six-membered cyclic epoxides (CHO and vCHO) proceeded faster than the five-membered cyclic epoxide (CPO).

[0381] Cyclopentene oxide is a particularly interesting epoxide monomer because polycarbonates of cyclopentene oxide exhibit the unusual depolymerization back to the monomer (instead of backbiting to trans-cyclopentene carbonate), thus making it possible to obtain recyclable polymers. The copolymerization of cyclopentene oxide with CO2 leads to 1 It showed excellent selectivity (95%) with trace amounts of cis-cyclopentene oxide (5%) as observed by H NMR spectroscopy (Table 4, entry 10). Under optimized conditions (0.025 mol% catalyst, 50 °C, 20 bar CO, neat CPO) for 162 h. -1 This represents a four-fold improvement in activity (42 h) compared to the best reported cobalt salen using a tethered quaternary ammonium salt. -1 , 0.1 mol% catalyst, 50 °C, 20 bar CO2), and its chromium derivatives (77 h -1 , 0.1 mol% catalyst, 70 °C, 20 bar CO2) showing a two-fold improvement in activity. 25 .

[0382] While specific embodiments of the present invention have been described herein for purposes of reference and example, various modifications will become apparent to those skilled in the art without departing from the scope of the invention, as set forth by the appended claims. References 1AM Chapman, C. Keyworth, M. R. Kember, A. J. J. Lennox, C. K. Williams, ACS Catal. 2015, 5, 1581-1588. 2 N. von der Assen, A. Bardow, Green Chem. 2014, 16, 3272-3280. 3 SH Lee, A. Cyriac, JY Jeon, BY Lee, Polym. Chem. 2012, 3, 1215. 4 J. Langanke, A. Wolf, J. Hofmann, K. Bohm, MA Subhani, TE Muller, W. Leitner, C. Gurtler, Green Chem. 2014, 16, 1865-1870. 5 T. Stosser, C. Li, J. Unruangsri, PK Saini, RJ Sablong, MAR Meier, CK Williams, C. Koning, Polym. Chem. 2017, 8, 6099-6105. 6 O. Hauenstein, M. Reiter, S. Agarwal, B. Rieger, A. Greiner, Green Chem. 2016, 18, 760-770. 7 DJ Darensbourg, Chem. Rev. 2007, 107, 2388-2410. 8 X.-B. Lu, DJ Darensbourg, Chem. Soc. Rev. 2012, 41, 1462-1484 9Z. Qin, CM Thomas, S. Lee, GW Coates, Angew. Fabric. Int. Ed. 2003, 42, 5484-5487. 10 Y. Wang, DJ Darensbourg, Coord. Fabric. Rev. Fr. 2018, 372, 85-100. 11 MI Childers, JM Longo, NJ Van Zee, AM LaPointe, GW Coates, Chem. Rev. Fr. 2014, 114, 8129-8152. 12 DJ Darensbourg, RM Mackiewicz, J. Am. Fabric. Soc. 2005, 127, 14026-14038. 13 CT Cohen, GW Coates, J. Polym. Ski. Arrive. Fabric. 2006, 44, 5182-5191. 14 PCB Widger, SM Ahmed, GW Coates, Macromolecules 2011, 44, 5666-5670. 15 DJ Darensbourg, JC Yarbrough, C. Ortiz, CC Fang, J. Am. Fabric. Soc. 2003, 125, 7586-7591. 16 EK Noh, SJ Na, S. S, S.-W. Kim, B.Y. Lee, J. Am. Fabric. Soc. 2007, 129, 8082-8083. 17 S. S, JK Min, JE Seong, SJ Na, BY Lee, Angew. Fabric. Int. Ed. 2008, 47, 7306-7309. 18C. J. Van Staveren, J. Van Eerden, F. C. J. M. Van Veggel, S. Harkema, D. N. Reinhoudt, J. Am. Chem. Soc. 1988, 110, 4994-5008. 19 Lu, X. B.; Shi, L.; Wang, Y. M.; Zhang, R.; Zhang, Y. J.; Peng, X. J.; Zhang, Z. C.; Li, B., Design of highly active binary catalyst systems for CO2 / epoxide copolymerization: Polymer selectivity, enantioselectivity, and stereochemistry control. J. Am. Chem. Soc. 2006, 128 (5), 1664-1674. 20 Darensbourg, D. J.; Wu, G. P., A One-Pot Synthesis of a Triblock Copolymer from Propylene Oxide / Carbon Dioxide and Lactide: Intermediacy of Polyol Initiators. Angew. Chem. Int. Ed. 2013, 52 (40), 10602-10606. 21 Nakano, K.; Kamada, T.; Nozaki, K., Selective formation of polycarbonate over cyclic carbonate: Copolymerization of epoxides with carbon dioxide catalyzed by a cobalt(III) complex with a piperidinium end-capping arm. Angew. Chem. Int. Ed. 2006, 45 (43), 7274-7277. 22Cyriac, A.; Lee, S. H.; Varghese, J. K.; Park, E. S.; Park, J. H.; Lee, B. Y., Immortal CO2 / Propylene Oxide Copolymerization: Precise Control of Molecular Weight and Architecture of Various Block Copolymers. Macromolecules 2010, 43 (18), 7398-7401. 23 Patil, N. G.; Boopathi, S. K.; Alagi, P.; Hadjichristidis, N.; Gnanou, Y.; Feng, X., Carboxylate Salts as Ideal Initiators for the Metal-Free Copolymerization of CO2 with Epoxides: Synthesis of Well-Defined Polycarbonates Diols and Polyols. Macromolecules 2019, 52 (6), 2431-2438. 24 Gao, Y.; Gu, L.; Qin, Y.; Wang, X.; Wang, F., Dicarboxylic acid promoted immortal copolymerization for controllable synthesis of low-molecular weight oligo(carbonate-ether) diols with tunable carbonate unit content. J. Polym. Sci, Part A: Polym. Chem. 2012, 50 (24), 5177-5184. 25Darensbourg, D. J., Yeung, A. D. & Wei, S.-H. Base initiated depolymerization of polycarbonates to epoxide and carbon dioxide co-monomers: a computational study. Green Chemistry, 2013, 15, 1578-1583

Claims

1. 1. A method for preparing a polycarbonate, said method comprising: a) contacting carbon dioxide with at least one epoxide Including, Step a) is the reaction of a compound of formula I shown below: 【Chemistry 147】 (In the formula, M １ is selected from the group consisting of Group 2 metals, Group 3 metals, transition metals, Group 13 metals, Group 14 metals and lanthanides; M ２ is selected from Li, Na, K, Rb, Cs, Sr, Ba, Y, Ln, Al, Ga and Sn; R １ is selected from (2-5C)alkylene, (2-5C)alkenylene and (2-5C)alkynylene, wherein 0, 1 or 2 carbon atoms in any one of said (2-5C)alkylene, (2-5C)alkenylene and (2-5C)alkynylene are replaced by a heteroatom selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C)alkylene, (2-5C)alkenylene and (2-5C)alkynylene are replaced by one or more R ｘ and optionally substituted independently by R ｘ are respectively halo, hydroxy, cyano, nitro, (1-20C) alkyl, (2-20C) alkenyl, (2-20C) alkynyl, (1-20C) haloalkyl, (1-20C) alkoxy, aryl, heteroaryl and —NR ｘａ R ｘｂ and R ｘ Any of the aryl or heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-20C)alkyl, (1-20C)haloalkyl, and (1-20C)alkoxy; ｘａ and R ｘｂ are independently selected from hydrogen and (1-3C) alkyl; and / or Two or more R's located on adjacent atoms ｘ are linked to each other so that, when taken together with the atoms to which they are attached, they form a monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring system, any of said monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring systems being optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-20C)alkyl, (1-20C)haloalkyl and (1-20C)alkoxy; R ２ are each absent, hydrogen, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R ２ａ , —C(O)—OR ２ａ and —C(O)—NR ２ａ R ２ｂ and R ２ any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; ２ａ and R ２ｂ are independently selected from hydrogen and (1-3C)alkyl; X １ are -CH- and -CR ４ -, -CH ２ --, --CHR ４ -, -CR ４ R ４ － and -PR ４ R ４ -, and R ４ are each independently selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl; R ４ wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl and heteroaryl(1-2C)alkyl are optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy; E １ is C and E ２ is O, S or N, or E １ is N and E ２ is O, R ３ are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R ３ａ , —C(O)—OR ３ａ , -O-C(O)-R ３ａ , —C(O)—NR ３ａ R ３ｂ , -N(R ３ａ ) C(O)-R ３ｂ and -NR ３ａ R ３ｂ and R ３ any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; ３ａ and R ３ｂ are independently selected from hydrogen and (1-3C) alkyl; and / or Two Rs located on adjacent atoms ３ are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; each n is independently selected from 0, 1, 2, and 3; L １ and L ２ is absent, halo, nitrate, hydroxy, (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, heteroaryl(1-3C)alkyl, —O—C(O)—R ａ , -O-C(O)OR ａ , -OP(O)(R ａ ) ２ , -P(O)(OR ａ ) ２ , -OR ａ , —O—S(O) ２ -Ra, -OS(O)-(R ａ ) ２ , -OS(O)-R ａ , -S(O)-R ａ , -S-C(O)-R ａ , -S-C(S)-OR ａ , -N(H)S(O) ２ -Ra, -N-(S(O) ２ -R ａ ) 2, -S-R ａ , -N(R ａ )-C(O)-R ａ , -C(O)-N(R ａ ) ２ , -N(R ａ ) ２ and —O—Si(R ａ ) ｘ (OR ａ ) ｙ where x and y are independently 0, 1, 2, or 3, with the proviso that x+y=3; １ or L ２ Any of the (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl and heteroaryl(1-3C)alkyl may be optionally substituted with one or more R ｂ and optionally substituted by, with the proviso that L １ and L ２ provided that at least one of R ａ is independently selected from hydrogen, (1-25C)alkyl, (2-25C)alkenyl, (2-25C)alkynyl, (1-25C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, and heteroaryl(1-3C)alkyl; R ａ any (1-25C)alkyl, (2-25C)alkenyl, (2-25C)alkynyl, (1-25C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, or heteroaryl(1-3C)alkyl occurring in R is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; ｂ are each independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; G １ and G ２ is independently selected from absent and a neutral or anionic donor ligand that is a Lewis base; Q has the structure Q-I or Q-II shown below: 【Chemistry 148】 and X ２ are each independently absent or (1-3C)alkylene, said (1-3C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; X ３ are each independently absent or (1-3C)alkylene, said (1-3C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; X ４ each independently is absent or methylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; m is 1, 2, 3 or 4; R ５ are each hydrogen, halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R ５ａ , —C(O)—OR ５ａ , -O-C(O)-R ５ａ , —C(O)—NR ５ａ R ５ｂ , -N(R ５ａ ) C(O)-R ５ｂ and -NR ５ａ R ５ｂ and R ５ any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; ５ａ and R ５ｂ are independently selected from hydrogen and (1-3C) alkyl; and / or Two Rs located on adjacent atoms ５ are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; R ６ are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, (1-4C) alkoxy, aryl, aryl(1-2C) alkyl, heteroaryl, heteroaryl(1-2C) alkyl, -C(O)-R ６ａ , —C(O)—OR ６ａ , -O-C(O)-R ６ａ , —C(O)—NR ６ａ R ６ｂ , -N(R ６ａ ) C(O)-R ６ｂ and -NR ６ａ R ６ｂ and R ６ any of the aryl, aryl(1-2C)alkyl, heteroaryl, and heteroaryl(1-2C)alkyl groups are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; ６ａ and R ６ｂ are independently selected from hydrogen and (1-3C) alkyl; and / or Two Rs located on adjacent atoms ６ are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring system, any of said monocyclic aromatic, heteroaromatic, carbocyclic, or heterocyclic ring systems being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; each p is independently selected from 0, 1, 2, or 3; R ７ are each independently selected from hydrogen or (1-3C) alkyl. A method carried out in the presence of

2. M １ 2. The method of claim 1, wherein is selected from Co, Fe, Cr, Ni, Al, Ti and Zn.

3. R １ has a structure according to Formula A shown below: 【Chemistry 149】 (In the formula, W １ , W ２ , W ３ , W ４ and W ５ does not exist, -CH ２ -, -NH-, and -O-; however, i) W １ , W ２ , W ３ , W ４ and W ５ Three or fewer of these are not present, ii) W １ , W ２ , W ３ , W ４ and W ５ At least two of the ２ - and iii) —NH— is not adjacent to —O—; Provided that, -CH ２ - any of the following may contain one or two R ｘ and any —NH— is optionally substituted by one R ｘ and R ｘ are respectively halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, (1-4C) alkoxy, phenyl, 5-6 membered heteroaryl and —NR ｘａ R ｘｂ and R ｘ Any of the phenyl or 5- to 6-membered heteroaryl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl, and (1-4C)alkoxy; ｘａ and R ｘｂ are independently selected from hydrogen and (1-3C) alkyl; and / or two or more R located on adjacent atoms ｘ are linked to each other so that, when taken together with the atoms to which they are attached, they form a 5- to 7-membered monocyclic or 8- to 10-membered bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring system, any of said 5- to 7-membered monocyclic or 8- to 10-membered bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring systems optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy.

3. The method of claim 1 or 2, comprising:

4. R １ has any one of the following structures: [Chemical 150] The method according to any one of claims 1 to 3, comprising:

5. R ２ are absent, hydrogen, (1-3C) alkyl, phenyl, benzyl, and —C(O)—NR ２ａ R ２ｂ and R ２ wherein either phenyl or benzyl is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; ２ａ and R ２ｂ The method of any one of claims 1 to 4, wherein is independently selected from hydrogen and (1-2C) alkyl.

6. X １ are -CH- and -CR ４ -, -CH ２ --, --CHR ４ - and - CR ４ R ４ － and R ４ are each independently selected from (1-2C)alkyl and phenyl; R ４ 6. The method of any one of claims 1 to 5, wherein any phenyl in is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl and (1-2C)alkoxy.

7. E １ is C and E ２ The method of any one of claims 1 to 6, wherein is O.

8. R ３ are respectively halo, hydroxy, cyano, nitro, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, phenyl and —NR ３ａ R ３ｂ and R ３ any phenyl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, and (1-2C) alkoxy; ３ａ and R ３ｂ are independently selected from hydrogen and (1-3C)alkyl; each n is independently selected from 0, 1 and 2; The method according to any one of claims 1 to 7.

9. L １ and L ２ is absent and —O—C(O)—R ａ and R ａ The method according to any one of claims 1 to 8, wherein is (1-20C) alkyl or (2-25C) alkenyl.

10. G １ and G ２ The method of any one of claims 1 to 9, wherein

11. X ２ are each independently absent or methylene, said methylene being optionally substituted with one or two groups independently selected from (1-2C)alkyl; X ３ are each independently absent or (1-2C)alkylene, said (1-2C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; X ４ are each independently methylene optionally substituted with one or two methyl groups; The method according to any one of claims 1 to 10.

12. 12. The method of any one of claims 1 to 11, wherein m is 2.

13. R ５ are respectively hydrogen, halo, hydroxy, (1-3C) alkyl, (1-3C) haloalkyl, (1-3C) alkoxy, phenyl, phenyl(1-2C) alkyl and —NR ５ａ R ５ｂ and R ５ wherein any of the phenyl and phenyl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl, and (1-2C)alkoxy; ５ａ and R ５ｂ are independently selected from hydrogen and (1-2C) alkyl; and / or two R located on adjacent atoms ５ are linked to each other so that, when taken together with the atoms to which they are attached, they form a benzene or a 5- to 6-membered heteroaromatic ring, any of said benzene and 5- to 6-membered heteroaromatic rings being optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C)alkyl, (1-2C)haloalkyl and (1-2C)alkoxy; The method according to any one of claims 1 to 12.

14. R ６ are respectively halo, hydroxy, cyano, nitro, (1-2C) alkyl, (1-2C) haloalkyl, (1-2C) alkoxy, phenyl and —NR ６ａ R ６ｂ and R ６ any phenyl in R is optionally substituted with one or more groups independently selected from halo, hydroxy, (1-2C) alkyl, (1-2C) haloalkyl, and (1-2C) alkoxy; ６ａ and R ６ｂ are independently selected from hydrogen and (1-3C)alkyl; each p is independently selected from 0 and 1; The method according to any one of claims 1 to 13.

15. R ７ The method of any one of claims 1 to 14, wherein is independently selected from hydrogen or methyl.

16. 16. The method of any one of claims 1 to 15, wherein Q is QI.

17. Q is any of the following structures: 【Chemistry 151】 The method according to any one of claims 1 to 16, comprising:

18. The compound of formula I has a structure according to any of the following: 【Chemistry 155】 【Chemistry 156】 【Chemistry 157】 【Chemistry 158】 【Chemistry 159】 The method according to any one of claims 1 to 17, comprising:

19. 19. The method of any one of claims 1 to 18, wherein the epoxide is selected from ethylene oxide, propylene oxide, vinyl-propylene oxide, butylene oxide, allyl glycidyl ether, tert-butyl glycidyl ether, epichlorohydrin, styrene oxide, cyclohexene oxide, vinyl-cyclohexene oxide, cyclopentene oxide, limonene oxide, and mixtures of two or more thereof.

20. 20. The method of any one of claims 1 to 19, wherein the epoxide is propylene oxide or cyclohexene oxide.

21. The process according to any one of claims 1 to 20, wherein step a) is carried out in the presence of a chain transfer agent.

22. Step a) is performed by subjecting the ２ The process according to any one of claims 1 to 21, wherein the process is carried out at a pressure of

23. The method according to any one of claims 1 to 22, wherein step a) is carried out at a temperature of from 0 to 250°C.

24. A compound having a structure according to Formula I ： 【Chemistry 147】 (In the formula, M 1 is selected from the group consisting of Group 2 metals, Group 3 metals, transition metals, Group 13 metals, Group 14 metals and lanthanides; M2 is selected from Li, Na, K, Rb, Ca, Sr, Ba, Y, Ln, Al, Ga and Sn; R 1 is selected from (2-5C)alkylene, (2-5C)alkenylene and (2-5C)alkynylene, wherein 0, 1 or 2 carbon atoms in any one of said (2-5C)alkylene, (2-5C)alkenylene and (2-5C)alkynylene are replaced by heteroatoms selected from O and N, and any of the carbon atoms, O atoms or N atoms in said (2-5C)alkylene, (2-5C)alkenylene and (2-5C)alkynylene may be optionally substituted independently by one or more R x ; each R x is independently selected from halo, hydroxy, cyano, nitro, (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)haloalkyl, (1-20C)alkoxy, aryl, heteroaryl and -NR xa R xb , wherein any aryl or heteroaryl in R x is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-20C)alkyl, (1-20C)haloalkyl and (1-20C)alkoxy, and R xa and R xb are independently selected from hydrogen and (1-3C)alkyl; and / or two or more R x s located on adjacent atoms are linked to each other so that, when taken together with the atoms to which they are attached, they form a monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring system, any of said monocyclic or bicyclic aromatic, heteroaromatic, carbocyclic or heterocyclic ring systems optionally substituted by one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-20C)alkyl, (1-20C)haloalkyl and (1-20C)alkoxy; each R 2 is independently selected from absent, hydrogen, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl, aryl(1-2C)alkyl, heteroaryl, heteroaryl(1-2C)alkyl, —C(O)—R 2a , —C(O)—OR 2a and —C(O)—NR 2a R 2b , wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl and heteroaryl(1-2C)alkyl in R 2 is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy, and R 2a and R 2b are independently selected from hydrogen and (1-3C)alkyl; each X 1 is independently selected from —CH—, —CR 4 —, —CH 2 —, —CHR 4 —, —CR 4 R 4 — and —PR 4 R 4 —; each R 4 is independently selected from (1-4C) alkyl, (2-4C) alkenyl, (2-4C) alkynyl, (1-4C) haloalkyl, aryl, aryl(1-2C) alkyl, heteroaryl, and heteroaryl(1-2C) alkyl; any of the aryl, aryl(1-2C) alkyl, heteroaryl, and heteroaryl(1-2C) alkyl in R 4 is optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, and (1-4C) alkoxy; E 1 is C and E 2 is O, S or N, or E 1 is N and E 2 is O; each R 3 is independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryl(1-2C)alkyl, heteroaryl, heteroaryl(1-2C)alkyl, —C(O)—R 3a , —C(O)—OR 3a , —O—C(O)—R 3a , —C(O)—NR 3a R 3b , —N(R 3a )C(O)—R 3b and —NR 3a R 3b ; R 3 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl and heteroaryl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy; and R 3a and R 3b are independently selected from hydrogen and (1-3C)alkyl. and / or two R 3 s located on adjacent atoms are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic ring system, a heteroaromatic ring system, a carbocyclic ring system, or a heterocyclic ring system, any of said monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, and (1-4C) alkoxy; each n is independently selected from 0, 1, 2, and 3; L 1 and L 2 are absent, halo, nitrate, hydroxy, (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, heteroaryl(1-3C)alkyl, —O—C(O)—R a , —O—C(O)O—R a , —OP(O)(R a ) 2 , —P(O)(OR a ) 2 , —OR a , —O—S(O) 2 —R a , —O—S(O)—(R a ) 2 , —O—S(O)—R a , —S(O)—R a , —S—C(O)—R a , —S—C(S)—O—R a , —N(H)S(O) 2 —R a , —N—(S(O) 2 —R a ) 2 , —S—R a , —N(R a )—C(O)—R a , —C(O)—N(R a ) 2 , —N(R a ) 2 and —O—Si(R a ) x (OR a ) y (x and y are independently 0, 1, 2 or 3, with the proviso that x+y=3); L 1 or L 2 any of said (1-20C)alkyl, (2-20C)alkenyl, (2-20C)alkynyl, (1-20C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl and heteroaryl(1-3C)alkyl being optionally substituted by one or more R b , provided that L 1 is present; R a is independently selected from hydrogen, (1-25C)alkyl, (2-25C)alkenyl, (2-25C)alkynyl, (1-25C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl and heteroaryl(1-3C)alkyl; any (1-25C)alkyl, (2-25C)alkenyl, (2-25C)alkynyl, (1-25C)heteroaliphatic, carbocyclyl, carbocyclyl(1-3C)alkyl, heterocyclyl, heterocyclyl(1-3C)alkyl, aryl, aryl(1-3C)alkyl, heteroaryl, or heteroaryl(1-3C)alkyl occurring in R b is independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; are each independently substituted by one or more groups independently selected from halo, cyano, nitro, amino, hydroxy, (1-4C)alkyl, (1-4C)haloalkyl, (2-4C)alkenyl, (2-4C)alkynyl, and (1-4C)alkoxy; G 1 and G 2 are independently selected from absent and neutral or anionic donor ligands that are Lewis bases; Q has the structure Q-I or Q-II shown below: 【Chemistry 148】 and each X 2 is independently absent or (1-3C)alkylene, said (1-3C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; each X 3 is independently absent or (1-3C)alkylene, said (1-3C)alkylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; each X 4 is independently absent or methylene optionally substituted with one or two groups independently selected from (1-2C)alkyl; m is 1, 2, 3 or 4; each R 5 is independently selected from hydrogen, halo, hydroxy, cyano, nitro, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryl(1-2C)alkyl, heteroaryl, heteroaryl(1-2C)alkyl, —C(O)—R 5a , —C(O)—OR 5a , —O—C(O)—R 5a , —C(O)—NR 5a R 5b , —N(R 5a )C(O)—R 5b and —NR 5a R 5b ; R 5 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl and heteroaryl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy; and R 5a and R 5b are independently selected from hydrogen and (1-3C)alkyl. and / or two R 5 s located on adjacent atoms are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic ring system, a heteroaromatic ring system, a carbocyclic ring system, or a heterocyclic ring system, any of said monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, and (1-4C) alkoxy; Each R 6 is independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryl(1-2C)alkyl, heteroaryl, heteroaryl(1-2C)alkyl, —C(O)—R 6a , —C(O)—OR 6a , —O—C(O)—R 6a , —C(O)—NR 6a R 6b , —N(R 6a )C(O)—R 6b and —NR 6a R 6b ; R 6 wherein any of the aryl, aryl(1-2C)alkyl, heteroaryl and heteroaryl(1-2C)alkyl are optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy; and R 6a and R 6b are independently selected from hydrogen and (1-3C)alkyl. and / or two R 6 s located on adjacent atoms are linked to each other so that, when taken together with the atom to which they are attached, they form a monocyclic aromatic ring system, a heteroaromatic ring system, a carbocyclic ring system, or a heterocyclic ring system, any of said monocyclic aromatic ring system, heteroaromatic ring system, carbocyclic ring system, or heterocyclic ring system being optionally substituted with one or more groups independently selected from halo, hydroxy, cyano, nitro, (1-4C) alkyl, (1-4C) haloalkyl, and (1-4C) alkoxy; each p is independently selected from 0, 1, 2, or 3; Each R 7 is independently selected from hydrogen or (1-3C) alkyl).

25. The compound of claim 24, wherein the compound is as defined in any one of claims 2 to 18, provided that L 1 is present.

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