Non-cryogenic synthesis of heteroatom-bridged precursors for metal-ligand complex catalysts

Abstract

Embodiments include metal-ligand complex catalyst precursors, (L 1 )(L 2 )X(R 1 )(R 2 ), as well as the formula Q2X(R 1 )(R 2 ) from the compound of formula L 1 and L 2 independently, -R 3 -Z 1 or -R 4 -Z 1 R 1 and R 2 is a hydrogen atom, (C1 to C 40 ) hydrocarbyl, and optionally R 1 and R 2 are linked to form a ring having 3 to 50 atoms, excluding hydrogen atoms, in the ring. X is Si, Ge, Sn, or Pb. Each Q is independently Ar 1 -Y 1 -R 3 - or Ar 2 -Y 2 -R 4 -R 3 and R 4 is -(CR C 2) m m is 1 or 2; and each R C is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, and —H. Y 1 and Y 2 are independently S, Se, or Te. 1 and Ar 2 are independently (C6~C 50 ) aryl. Ar 1 -Y 1 -R 3 - and Ar 2 -Y 2 -R 4 - are not the same. Each Z 1 are independently selected from Cl, Br, and I.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 62 / 980,655, filed February 24, 2020, the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THE INVENTION FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more particularly to precursors to metal-ligand complex catalyst systems for olefin polymerization and methods of making the precursors. [Background technology]

[0003] Olefin-based polymers, such as ethylene-based polymers and / or propylene-based polymers, are produced via various catalyst systems. The selection of such catalyst system used in the polymerization process of an olefin-based polymer is an important factor that contributes to the characteristics and properties of such an olefin-based polymer.

[0004] Ethylene- and propylene-based polymers are manufactured for a wide variety of articles. Ethylene-based polymer polymerization processes can be varied in several ways to produce a wide variety of resulting polyethylene resins with different physical properties that make the various resins suitable for use in different applications.

[0005] The chemical industry strives to develop catalyst systems comprising metal-ligand complexes that have improved selectivity between comonomer and ethylene under olefin polymerization reaction conditions (e.g., temperature). The catalyst systems could be capable of conducting polymerization reactions that provide new compositions of matter (e.g., new polyolefin compositions), improve reaction yields, provide alternative substrate selectivities (e.g., provide new relative selectivities for monomer and comonomer in the production of polyolefin copolymers), improve process safety, or a combination thereof.

[0006] An exemplary type of metal-ligand complex, the heteroatom-bridged bis(biphenylphenoxy) catalyst system, has shown promise in commercial plants across multiple production platforms. However, current synthesis of heteroatom bridges requires cryogenic conditions, e.g., reaction temperatures of −78°C, which poses significant costs for large-scale production. Summary of the Invention

[0007] There is a continuing need for practical and cost-effective methods for preparing heteroatom bridges in high yield under non-cryogenic conditions. According to an embodiment, Q2X(R 1 )(R 2 ) is provided. 1 and R 2 is a hydrogen atom, (C1 to C 40 ) hydrocarbyl, and optionally R 1 and R 2 are linked to form a ring having 3 to 50 atoms, excluding hydrogen atoms, in the ring. X is Si, Ge, Sn, or Pb. Each Q is independently Ar 1 -Y 1 -R 3 - or Ar 2 -Y 2 -R 4 -R 3 and R 4 is -(CR C 2) m m is 1 or 2; and each R C is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, and —H; Y 1 and Y 2 are independently S, Se, or Te. 1 and Ar 2 are independently (C6~C 50 ) aryl. Ar 1 -Y 1 -R 3 - and Ar 2 -Y2 -R 4 - are not the same.

[0008] According to a twelfth aspect, a heteroatom-bridged precursor, (L 1 )(L 2 )X(R 1 )(R 2 The method for obtaining the compound of formula QX(R1)(R2) (wherein X, Q, R 1 , and R 2 is as defined above) to obtain a heteroatom-bridged precursor. 1 and L 2 independently, -R 3 -Z 1 or -R 4 -Z 1 and each Z 1 are independently selected from Cl, Br, and I.

[0009] Additional features and advantages of the described embodiments are set forth in the detailed description that follows, and in part will become readily apparent to those skilled in the art from the description, or may be learned by practice of the described embodiments, including the following detailed description and drawings and claims. DETAILED DESCRIPTION OF THE INVENTION

[0010] In the field of catalytic systems, examples of heteroatom bridges within procatalyst or catalyst molecules are generally represented by the formula (A):

[0011] [ka]

[0012] In formula (A), R 1 and R 2 is a hydrogen atom and (C1 to C 40Optionally, as indicated by the dashed line, R 1 and R 2 may be bonded to form a ring having 3 to 50 atoms, excluding hydrogen atoms, in the ring. In formula (A), X may be silicon (Si), germanium (Ge), tin (Sn), or lead (Pb). In formula (A), R 3 and R 4 is -(CR C 2) m -, where m is 1 or 2, and each R C is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, or —H. R 3 and R 4 All R in C is -H, for example, R 3 and R 4 can be methylene or ethane-1,2-diyl. 3 and R 4 The wavy line extending from represents the attachment of the heteroatom bridge to the main portion of the procatalyst or catalyst molecule.

[0013] In small-scale and large-scale synthetic routes to preparing heteroatom-bridged procatalysts, the heteroatom bridge can be incorporated into the procatalyst or catalyst molecule in one or more steps. The steps can include reacting an intermediate compound of the procatalyst or catalyst with a heteroatom-bridged precursor. An exemplary class of heteroatom-bridged precursors includes those represented by formula (1):

[0014] [ka]

[0015] In formula (1), X is selected from Si, Ge, Sn, and Pb. 1 and R 2 is a hydrogen atom and (C1 to C 40Optionally, R 1 and R 2 are linked to form a ring having 3 to 50 atoms in the ring, excluding hydrogen atoms.

[0016] The group L in the compound of formula (1) 1 and L 2 may be identical to each other, in which case the compound 1 and L 2 It is symmetric with respect to L. 1 and L 2 The two groups may be different from each other, in which case the compound is 1 and L 2 It is asymmetric with respect to L 1 and L 2 Compounds of formula (1) which are either symmetric or asymmetric with respect to the two moieties of 1 and L 2 However, the same group Z 1 -R 3 -, whereas in asymmetric compounds, L 1 But Z 1 -R 3 - and L 2 But Z 1 -R 4 - and Z 1 -R 3 - and Z 1 -R 4 - but not the same as Z 1 It may be possible to distinguish between R and R in that R is selected from chlorine (Cl), bromine (Br), and iodine (I). 3 and R 4 is -(CR C 2) m m is 1 or 2; and each R C is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, and —H.

[0017] Therefore, the group L 1 and L 2With respect to the compounds of formula (1), the compounds include symmetric compounds of formula (1A) and asymmetric compounds of formula (1B), as follows: all variables in both formulas are defined as in formula (1), and all variables having multiple occurrences in a single structure are identical in all occurrences.

[0018] [ka]

[0019] In some cases, the synthesis of heteroatom-bridged precursors may itself present challenges or require improvements, such as reduced cost or increased efficiency. As with any chemical synthesis, such improvements may be realized through the implementation of alternative synthetic strategies. Alternative synthetic strategies may involve performing the synthesis through different starting materials or intermediates.

[0020] Thus, embodiments of the present disclosure include compounds whose uses may include serving as intermediates for preparing, providing, or synthesizing heteroatom-bridged precursors, such as those having formula (1) as described above. Further embodiments of the present disclosure include synthetic methods for preparing heteroatom-bridged precursors. The synthetic methods incorporate the intermediate compounds in a reaction step during preparation.

[0021] Specific embodiments of intermediate compounds for heteroatom-bridged precursors are now described. It should be understood that the intermediate compounds of the present disclosure may be embodied in different forms and should not be construed as being limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0022] The intermediate compound according to an embodiment has the formula (3):

[0023] [ka]

[0024] In formula (3), R 1 and R 2 is a hydrogen atom, (C1 to C 40 ) hydrocarbyl, and optionally R 1 and R 2 are joined to form a ring having 3 to 50 atoms in the ring, excluding hydrogen atoms; X is Si, Ge, Sn, or Pb; and each Q is independently Ar 1 -Y 1 -R 3 - or Ar 2 -Y 2 -R 4 Among the various components of Q in equation (3), R 3 and R 4 is -(CR C 2) m m is 1 or 2; and each R C is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, and —H. Y 1 and Y 2 are independently S, Se, or Te. 1 and Ar 2 are independently (C6~C 50 ) aryl.

[0025] The two groups Q in the compound of formula (3) may be identical to each other, in which case the compound is symmetrical with respect to Q. Alternatively, the two groups Q may be different from each other, in which case the compound is asymmetrical with respect to Q. A compound of formula (3) that is either symmetrical or asymmetrical with respect to the two moieties Q is a symmetrical compound in which both groups Q are linked to the same group Ar 1 -Y 1 -R 3 -, while in asymmetric compounds, one Q is Ar 1 -Y 1 -R 3 - and the other Q is Ar 2 -Y 2 -R 4 - and Ar 1-Y 1 -R 3 - and Ar 2 -Y 2 -R 4 - may be distinguishable in that they are not identical. Thus, with respect to the group Q, compounds of formula (3) include symmetric compounds of formula (3A) and asymmetric compounds of formula (3B), as follows: all variables in both formulas are as defined in formula (3), and all variables having multiple occurrences in a single structure are identical in all occurrences.

[0026] [ka]

[0027] As will be explained in more detail subsequently, the heteroatom-bridged precursor of formula (1) can be prepared by converting a compound of formula (2) into an intermediate compound of formula (3). In this regard, it should be understood that the intermediate compound of formula (3) includes compounds of formulas (3A) and (3B). From the intermediate compound, a leaving group -Y 1 -Ar 1 and / or -Y 2 -Ar 2 is the Z from the metal halide 1 to give the heteroatom-bridged precursor of formula (1). The compound of formula (2) is:

[0028] [ka]

[0029] In formula (2), X and R 1 , and R 2 is described above with respect to equations (1) and (3), and Z 2 and Z 3 is independently selected from Cl, Br, I, and triflate.

[0030] In one or more embodiments, R 1 and R 2are independently a hydrogen atom or (C1 to C 20 ) Alkyl, (C3-C 20 ) cycloalkyl, or (C6-C 20 ) aryl (C1-C 40 ) hydrocarbyl. In some embodiments, R 1 and R 2 is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 1 and R 2 is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0031] Common abbreviations are listed below.

[0032] R 1 , R 2 , R 3 , R 4 , X, Y 1 , Y 2 , Z 1 , Z 2 , Z 3 , Ar 1 , Ar 2, and m: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; i-Pr: isopropyl; t-Bu: tert-butyl; t-Oct: tert-octyl(2,4,4-trimethylpentan-2-yl); Tf: trifluoromethanesulfonate; THF: tetrahydrofuran; Et2O: diethyl ether; CHCl: dichloromethane; C6D6: deuterated benzene or benzene-d6; CDCl3: deuterated chloroform; BHT: butylated hydroxytoluene; TCB: 1,2,4-trichlorobenzene; MgSO4: magnesium sulfate; n-BuLi: butyllithium; HfCl4: hafnium(IV) chloride; HfBn4: hafnium(IV) tetrabenzyl; ZrCl4: salt Zirconium(IV) chloride; ZrBn4: zirconium(IV) tetrabenzyl; ZrBn2Cl2(OEt2): zirconium(IV) dibenzyl dichloride mono-diethyl etherate; HfBn2Cl2(OEt2): hafnium(IV) dibenzyl dichloride mono-diethyl etherate; N2: nitrogen gas; PhMe: toluene; PPR: parallel pressure reactor; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; TEA: triethylamine; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimole; M: molar solution; mM: millimolar solution; mL or ml: milliliter; min or mins: minutes; h or hrs: hours; d: days; RT: room temperature.

[0033] The term "independently selected" refers to 1 , R 2 , R 3 , and R 4 and the like may be the same or different (e.g., R 1 , R 2 , R 3 , and R 4 may all be substituted alkyl, or R 1 and R 2 may be cyclic alkyl, R 3 and R 4The term "substituted alkyl" is used herein to indicate that the substituent is a substituted alkyl, and the like. Chemical names associated with substituents are intended to convey chemical structures recognized in the art as corresponding to the chemical structure of the chemical name. Thus, chemical names are intended to supplement and illustrate, not preclude, structural definitions known to those of skill in the art.

[0034] When used to describe certain carbon atom-containing chemical groups, "(C x ~C y A bracketed expression having the form "(C1-C)" means that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive, including x and y. For example, (C1-C 40 ) Hydrocarbyl is a hydrocarbyl group having 1 to 40 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are S The parenthesized "(C x ~C y )" for the chemical group R S Substituted versions may be formed by adding any group R S Depending on the identity of "R", the group may contain more than y carbon atoms. For example, "R S exactly one group R is phenyl (-C6H5) S (C1~C 40 )alkyl" can contain from 7 to 46 carbon atoms. Therefore, the parenthesized "(C x ~C y )" is a group defined using one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group are the minimum and maximum total numbers of carbon atoms in both x and y, and all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0035] In some embodiments, the heteroatom bridge precursor chemical group of formula (1) (i.e., R 1 , Ar 1 etc.) are R SIn other embodiments, at least one of the chemical groups of the heteroatom bridge precursor of formula (1) independently comprises one or more R S In some embodiments, the R in the chemical group of the heteroatom bridge precursor of formula (1) S The total number of R in the chemical group of the heteroatom bridge precursor of formula (1) does not exceed 20. S The total number of R does not exceed 10. For example, each R 1~4 and Ar 1 But two R S When substituted with Ar 2 is R S In an embodiment where the total number of R S In another embodiment, the R in the chemical group of the heteroatom bridge precursor of formula (1) S The total number of R S May not exceed two or three R S are attached to the same chemical group of the heteroatom-bridged precursor of formula (1), each R S are independently attached to the same or different carbon atoms or heteroatoms and may include per-substitution of chemical groups.

[0036] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "persubstituted" means that all hydrogen atoms (-H) bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by a substituent (e.g., R S The term "polysubstituted" means that at least two, but fewer than all, of the hydrogen atoms bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group are substituted with a substituent (e.g., R S ) is meant to be replaced by

[0037] The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0038] "(C1~C 40 The term "hydrocarbyl" means a hydrocarbon radical having from 1 to 40 carbon atoms, wherein each hydrocarbon radical is aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having 3 or more carbon atoms, including monocyclic and polycyclic, fused and non-fused polycyclic, including bicyclic) or acyclic, and is substituted with one or more R S or is unsubstituted.

[0039] In the present disclosure, (C1 to C 40 ) Hydrocarbyl is unsubstituted or substituted (C1-C 40 ) Alkyl, (C3-C 40 ) cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 ) alkylene, such as benzyl (—CH2—C6H5).

[0040] "(C1~C 40 The term "alkyl" refers to a group that is unsubstituted or has one or more R S means a saturated straight or branched chain hydrocarbon radical having 1 to 40 carbon atoms, substituted with unsubstituted (C1-C 40 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 12 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "(C1-C5) alkyl" (with brackets) means that there are up to 45 carbon atoms in the radical, including the substituents, e.g., one R S replaced by (C 27 ~C 40 Each (C1-C5) alkyl can be, for example, methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0041] "(C6~C 50 The term "aryl" refers to an aryl group having 6 to 50 carbon atoms, of which at least 6 to 14 carbon atoms are aromatic ring carbon atoms, unsubstituted or (one or more R S (by) a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring(s) of the aromatic radical may independently be fused or non-fused and aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl include unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18 )aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 40 Examples of aryl include substituted (C1-C 20 ) Aryl, substituted (C6-C 18)aryl, 2,4-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0042] "(C3~C 40 The term "cycloalkyl" refers to a group that is unsubstituted or has one or more R S means a saturated cyclic hydrocarbon radical having 3 to 40 carbon atoms, substituted with other cycloalkyl groups, such as (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3 to C 40 Examples of cycloalkyl are unsubstituted (C-C 20 ) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0043] "(C1~C 40 The term "alkylene" may be unsubstituted or may contain one or more R S means a saturated straight or branched diradical (i.e., the radical is not on a ring atom) having 1 to 40 carbon atoms, substituted by 40 Examples of alkylene are unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3 and -(CH2)4C * Unsubstituted (C1-C, including (H)(CH3) 20 ) alkylene, wherein "C* " represents a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 40 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, the two R S are combined together (C1~C 18 ) alkylene, so that the substituted (C1-C 50 Examples of )alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0044] "(C3~C 40 The term "cycloalkylene" may be unsubstituted or may contain one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) having 3 to 40 carbon atoms substituted by

[0045] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O), Si(R C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )-, and each R C and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or —H, and each R N is unsubstituted (C1 to C 18The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 40 The term "heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 40 carbon atoms. (C1-C 40 The heterohydrocarbon of the heterohydrocarbyl has one or more heteroatoms. The heterohydrocarbyl radical may be on a carbon atom or a heteroatom. Each (C1-C 40 ) heterohydrocarbyl is unsubstituted or (one or more R S They may be substituted (by), aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0046] (C1~C 40 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1-C 40 Non-limiting examples of heterohydrocarbyls include (C1-C 40 ) heteroalkyl, (C1-C 40 ) hydrocarbyl-O-, (C1-C 40 ) hydrocarbyl-S-, (C1-C 40 ) hydrocarbyl-S(O)-, (C1-C 40 ) hydrocarbyl-S(O)2-, (C1-C 40 ) Hydrocarbyl-Si(R C )2-, (C l ~C 40 )hydrocarbyl-N(R N )-, (C1~C 40 ) hydrocarbyl-P(R P )-, (C2~C 40 ) heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20) heteroalkylene, (C1-C 40 ) heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene may be mentioned.

[0047] "(C4~C 40 The term "heteroaryl" refers to a heteroaryl group that is unsubstituted or (one or more R S " refers to a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical having a total of 4 to 40 carbon atoms and 1 to 10 heteroatoms, substituted with (C4-C6). A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring(s) of the heteroaromatic radical may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C4-C6) 12 ) heteroaryl, etc. x ~C y ) heteroaryl (general heteroaryl) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or contains one or more R S The monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as being substituted with (I) or (II). The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and each heteroatom can be O, S, N, or P.

[0048] Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. 6-membered monocyclic heteroaromatic hydrocarbon radicals have 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatom can be N or P.

[0049] Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl.An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl.An example of a fused 6,6,6-ring system is acridine-9-yl.

[0050] (C1~C 40 The term heteroalkyl means a saturated straight or branched chain radical containing 1 to 40 carbon atoms and one or more heteroatoms. 40The term "hetero-alkylene" refers to a saturated straight or branched chain diradical containing 1 to 40 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or contains one or more R S has been replaced by

[0051] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0052] The term "halogen atom" or "halogen" means a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to a radical of a fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I - ) refers to the anionic form of a halogen atom.

[0053] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be substituted by a substituent R S The term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds (in heteroatom-containing groups), and the substituent R S This means that the aromatic ring or heteroaromatic ring does not contain any double bonds that may be present in the ring (if present), or in the aromatic or heteroaromatic ring (if present).

[0054] In embodiments, the heteroatom-bridged precursor of Formula (1) can be produced, for example, according to Reaction Scheme 1 or Reaction Scheme 2. Reaction Scheme 1 describes the preparation of a symmetric heteroatom-bridged precursor according to Formula (3A). Reaction Scheme 2 describes the preparation of an asymmetric heteroatom-bridged precursor according to Formula (3B). It should be understood that Reaction Schemes 1 and 2 are provided herein for illustrative purposes only and are not intended to limit any other embodiments described herein.

[0055] [ka]

[0056] As presented in accordance with Reaction Scheme 1, or as may be modified for the preparation of symmetric heteroatom-bridged precursors, a method for obtaining heteroatom-bridged precursors from compounds according to formula (3) comprises reacting at least one alkyl halide, alkali metal halide, MZ, at 90°C to 150°C. 1and a compound according to formula (3) (including a compound according to formula (3A) or (3B), as described above). The reaction provides a heteroatom-bridged precursor having formula (1), as described above. In embodiments, at least one alkyl halide is HR 3 -h, HR 4 -h, or a combination thereof, wherein R 3 and R 4 is as defined in formulas (1) and (3), and h is a halide selected from Cl, Br, or I. For the avoidance of any doubt, the alkyl halides in Scheme 1 have the same R as present in compounds (1B), (3), and (4). 3 M may, but need not necessarily, be an alkali metal selected from lithium, sodium, potassium, rubidium, and cesium. In embodiments, M is lithium. Z 1 is as defined in equation (1).

[0057] In embodiments, an alkyllithium can be reacted with a compound of formula (4) and a compound of formula (4') to provide a compound of formula (5) and a compound of formula (5'), respectively.

[0058] The alkyllithium is not particularly limited and can be, for example, but not limited to, methyllithium, ethyllithium, isopropyllithium, n-butyllithium, isobutyllithium, t-butyllithium, 1,8-octyldilithium, 1,7,18-octadecyltrilithium, decyllithium, phenyllithium, or a combination of two or more thereof.

[0059] Optionally, the reaction of the alkyllithium with the compound of formula (4) and the compound of formula (4') can be carried out in the presence of a solvent. In embodiments, the solvent can be a polar aprotic solvent. Suitable polar aprotic solvents that can be utilized herein include, for example, glycol ethers, cyclic ethers, combinations thereof, and the like. Exemplary polar aprotic solvents include, but are not limited to, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxypropane, combinations thereof, and the like.

[0060] In embodiments, the reaction of the alkyllithium with the compound of Formula (4) and the compound of Formula (4') can be carried out in a reaction flask immersed in a bath at a temperature of 0° C. to 25° C., e.g., 1° C. to 24° C., 2° C. to 23° C., 3° ​​C. to 22° C., 4° C. to 21° C., 5° C. to 20° C., 6° C. to 19° C., 7° C. to 18° C., 8° C. to 17° C., 9° C. to 16° C., 10° C. to 15° C., 11° C. to 14° C., or even 12° C. to 13° C. That is, the bath can be at a temperature of 0° C., 1° C., 2° C., 3° ​​C., 4° C., 5° C., 6° C., 7° C., 8° C., 9° C., 10° C., 11° C., 12° C., 13° C., 14° C., 15° C., 16° C., 17° C., 18° C., 19° C., 20° C., 21° C., 22° C., 23° C., 24° C., 25° C., or any fraction thereof. It should be noted that the temperature of the reaction bath can vary within a range formed from any of the temperatures listed above to any of the temperatures listed above.

[0061] In embodiments, the alkyllithium, the compound of Formula (4), and the compound of Formula (4') can be reacted for 0.5 hours to 5 hours, 1 hour to 4 hours, or even 2 hours to 3 hours. That is, the reaction can be carried out over the course of 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or any fraction thereof.

[0062] The method for obtaining a heteroatom-bridged precursor from a compound according to formula (3) may further include preparing a compound of formula (3). In an exemplary embodiment, a compound of formula (5) and a compound of formula (5') may be reacted with a compound of formula (2) to obtain a compound of formula (3). In an exemplary embodiment, preparing a compound of formula (3) may involve reacting a compound having formula (2) with a compound of formula Q at 0°C to 5°C, as described above. 1 -Li, where Q 1 is defined as Ar 1 -Y 1 -R 3 -) or formula Q 1 a first lithium compound having the formula Q 1 is defined as Ar 1 -Y 1 -R 3 -) and formula Q 2 a second lithium compound having Q 2 is defined as Ar 2 -Y 2 -R 4 -) to obtain a compound of formula (3). Compounds of formula (2) may be prepared by any suitable synthetic technique available to one skilled in the art of organic chemistry.

[0063] In some embodiments, reacting a compound having Formula (2) with at least one lithium compound converts the compound having Formula (2) to a compound of Formula Q 1 with a single lithium compound having —Li, thereby forming a heteroatom-bridged precursor L having the formula (1). 1 and L 2 Both -R 3 -Z 1 and are identical. Such embodiments are applicable to the synthesis of symmetric heteroatom-bridged precursors according to formula (1A). In exemplary embodiments, R at all occurrences in formulas (1) and (3) 3 can be -CH2- or R at all occurrences in formulas (1) and (3).3 In one exemplary embodiment, with respect to formulas (1A), (2), and (3A), Z in formula (2) can be -CH2CH2-. 2 and Z 3 can be Cl and Y at all occurrences 1 can be S and R at all occurrences 3 can be -CH2-, and Ar in all occurrences 1 can be 4-methylphenyl.

[0064] In a further embodiment, reacting the compound having formula (2) with at least one lithium compound converts the compound having formula (2) to a compound of formula Ar 1 -Y 1 -R 3 -Li (compound (5)) and a compound having the formula Ar 2 -Y 2 -R 4 -Li (compound (5')), thereby forming a heteroatom bridge L having formula (1). 1 and L 2 Such an embodiment is applicable to the synthesis of asymmetric heteroatom-bridged precursors according to formula (1B).

[0065] In some embodiments, the method for obtaining a heteroatom-bridged precursor from a compound according to Formula (3) comprises the step of: 1 preparing a first lithium compound Q 1 -Li, a second lithium compound Q 2 In preparing the symmetric compound of formula (1A), only one lithium compound Q is prepared. 1 -Li is required for the conversion of compounds of formula (2) to compounds of formula (3) or (3A). Thus, a single lithium compound Q 1 The preparation of —Li is carried out by reacting an alkyllithium compound of the formula Ar with an alkyllithium compound at 0°C to 25°C. 1 -Y 1 -R 3-H (compound (4)) to form a single lithium compound Q 1 In the preparation of the asymmetric compound of formula (1B), however, two lithium compounds Q 1 -Li and Q 2 -Li may be required, where Q 1 and Q 2 are not identical. In an embodiment, the lithium compound Q 1 -Li and Q 2 One or both of the alkyllithium compounds of formula Ar can be prepared by carrying out at least one of the following: 1 -Y 1 -R 3 -H (compound (4)) to form a first lithium compound Q 1 and reacting an alkyllithium compound with a compound of the formula Ar 2 -Y 2 -R 4 -H (compound (4')) to form a first lithium compound Q 2 - To obtain Li.

[0066] Optionally, reacting the compound having formula (2) with at least one lithium compound to obtain a compound of formula (3) can be carried out in the presence of a solvent. In embodiments, the solvent can be a polar aprotic solvent. Suitable polar aprotic solvents that can be utilized herein include, for example, glycol ethers, cyclic ethers, combinations thereof, and the like. Exemplary polar aprotic solvents include, but are not limited to, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxypropane, combinations thereof, and the like. In embodiments, the same solvent used in the reaction of alkyllithium with compounds of formula (4) and formula (4') can be used in this reaction of compounds of formula (5) and formula (5') with compounds of formula (2).

[0067] In embodiments, the reaction of the compounds of Formula (5) and Formula (5') with the compound of Formula (2) can be carried out in a reaction flask immersed in a bath at a temperature of 0°C to 5°C, 1°C to 4°C, or even 2°C to 3°C. That is, the bath can be at a temperature of 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, or any fraction thereof. It should be noted that the temperature of the reaction bath can vary within a range formed from any of the temperatures listed above to any of the temperatures listed above.

[0068] In embodiments, the reaction of the compounds of Formula (5) and Formula (5') with the compound of Formula (2) can occur rapidly. For example, the reaction can be completed within 0.5 to 5 minutes, 1 to 4 minutes, or even 2 to 3 minutes. That is, the reagents can be allowed to react for 0.5 minutes, 1 minute, 1.5 minutes, 2 minutes, 2.5 minutes, 3 minutes, 3.5 minutes, 4 minutes, 4.5 minutes, 5 minutes, or any fraction thereof.

[0069] In embodiments, the compound of formula (3) can be prepared by reacting alkyl halides and alkyl metal halides (MZ 1 ) to give the heteroatom-bridged precursor of formula (1) and compounds of formula (4) and formula (4'). Compounds of formula (4) and formula (4') can be recycled to give compounds of formula (5) and formula (5'), respectively.

[0070] Optionally, this reaction can be carried out in the presence of a solvent. In embodiments, the solvent can be a polar aprotic solvent. Suitable polar aprotic solvents that can be used herein include, for example, ethers, amides, sulfones, phosphoramides, combinations thereof, and the like. Exemplary polar aprotic solvents include, but are not limited to, dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidinone, dioxane, acetonitrile, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxypropane, tetramethylene sulfone, hexamethylphosphoramide, combinations thereof, and the like.

[0071] In embodiments, the reaction of the compound of Formula (3) with an alkyl halide and a lithium halide can be carried out in a reaction flask immersed in a bath at a temperature of 90°C to 150°C, 95°C to 145°C, 100°C to 140°C, 105°C to 135°C, 110°C to 130°C, or even 115°C to 125°C. That is, the bath can be at a temperature of 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, or any fraction thereof. Note that the temperature of the reaction bath can vary within a range formed from any of the temperatures listed above. In embodiments, the reaction can be carried out in a bath having a temperature ranging from 115°C to 140°C or from 120°C to 140°C.

[0072] In embodiments, the compound of Formula (3), the alkyl halide, and the lithium halide can be reacted for 5 to 20 hours, 6 to 19 hours, 7 to 18 hours, 8 to 17 hours, 9 to 16 hours, 10 to 15 hours, 11 to 14 hours, or even 12 to 13 hours. That is, the reaction can be carried out over the course of 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, or any fraction thereof.

[0073] Alkyl halides are H-(CR C 2) m -h, where h is a halogen radical; R C and m is R 3 and R 4 In embodiments, the alkyl halide is as defined above for HR, such that reaction of the compound of formula (3) with the alkyl halide and lithium halide produces compounds of formula (4) and formula (4') as by-products. 3 -h and HR 4 -h, but this is not necessarily the case.

[0074] The metal halide may be selected from LiCl, LiBr, and LiI, and Z in the compound of formula (1) 1 is a source of

[0075] In an exemplary embodiment, a method for obtaining a heteroatom-bridged precursor from a compound according to formula (3) may include the synthetic route described above, wherein Z of formula (2) 2 and Z 3 is Cl.

[0076] In an exemplary embodiment, a method for obtaining a heteroatom-bridged precursor from a compound according to formula (3) may include the synthetic route described above, in which all occurrences of Y 1 and Y 2 is S.

[0077] In an exemplary embodiment, a method for obtaining a heteroatom-bridged precursor from a compound according to formula (3) may include the synthetic route described above, wherein Ar 1 and Ar 2 is independently selected from the group consisting of phenyl, 2-methylphenyl, 3-methylphenyl, and 4-methylphenyl.

[0078] In an exemplary embodiment, a method for obtaining a heteroatom-bridged precursor from a compound according to formula (3) may include the synthetic route described above, in which Ar at all occurrences 1 and Ar 2 is phenyl.

[0079] In an exemplary embodiment, a method for obtaining a heteroatom-bridged precursor from a compound according to formula (3) can include the synthetic route described above, where X is Si or Ge.

[0080] In an exemplary embodiment, a method for obtaining a heteroatom-bridged precursor from a compound according to formula (3) may include the synthetic route described above, wherein R 1 and R 2 are independently (C1~C 12 ) alkyl.

[0081] Catalysts for polyolefin synthesis The heteroatom-bridged precursors described hereinabove can be utilized to prepare metal-ligand complex catalysts that can be used in the polymerization of olefins, primarily ethylene and propylene. The metal-ligand complexes can be prepared from the heteroatom-bridged precursors, for example, according to exemplary synthetic procedures found in WO 2018 / 022975, the contents of which are incorporated herein by reference.

[0082] One or more features of the present disclosure will be illustrated in light of the following examples. [Example]

[0083] Example 1: Preparation of di-isopropyl(bis(p-tolylthio)methyl)silane

[0084] [ka]

[0085] A 500 mL flask was charged with 4-(methylthio)toluene (24.5 mL, 183 mmol) and 200 mL of THF. The flask was cooled to 0 °C under an inert atmosphere, and n-BuLi (67.2 mL, 175 mmol, 2.1 equiv.) was added dropwise rapidly. The pale yellow solution was stirred at this temperature for 1 h and then allowed to warm slowly to room temperature for 2 h. The reaction mixture was cooled again to 0 °C, and a solution of iPrSiCl in THF (50 mL) was added dropwise at 0 °C. After 1 min, MeOH (10 mL) was added to quench the reaction. The resulting mixture was diluted with ether (50 mL) and washed with brine. The organic layer was dried over MgSO, filtered through a short pad of silica gel, and concentrated under reduced pressure to give a yellow oil (approximately 37 g, >100% yield). Residual (4-methylthio)toluene and THF were identified in the crude mixture. Optionally, these impurities may be removed by fractional distillation.

[0086] 1H NMR (400MHz, CDCl3) δ1.16(d,J=8Hz,12H),1.24(m,2H),2.31(s,6H),2.35(s,4H),7.09(d,J=8Hz,4H),7.22(d,J=8Hz,4H). 13 C{ 1 H}NMR(100MHz, CDCl3)δ11.4,13.2,18.1,20.9,126.8,129.5,134.8,136.5.

[0087] Example 2: Preparation of bis(iodomethyl)diisopropylsilane

[0088] [ka]

[0089] In an inert atmosphere glovebox, a 300 mL Parr vessel was charged with crude diisopropyl(bis(p-tolylthio)methyl)silane (7.80 g, 20.1 mmol), iodomethane (30.0 mL, 481 mmol, 24 equiv.), lithium iodide (2.69 g, 20.1 mmol), and DMF (20 mL). The vessel was sealed in the glovebox and heated to 120 °C overnight. The vessel was cooled to room temperature using an ice bath, and a sample was taken to monitor the progress of the reaction. Upon completion, the contents of the vessel were poured into a 250 mL round-bottom flask, and the vessel was rinsed with 20 mL of CHCl. ​​The solvent was removed by rotary evaporation to give a dark residue, which was dissolved in 100 mL of hexane and washed with 3 x 200 mL of water. After the organic layer was isolated and dried over MgSO, the mixture was filtered and the solvent removed by rotary evaporation to give a deep orange residue (10.3 g, 88% yield based on NMR integral, 83% GC purity), which was vacuum distilled to remove (4-methylthio)toluene to give the crude product.

[0090] 1 H NMR (400MHz, CDCl3) δ1.13 (d, J=8Hz, 12H), 1.32 (m, 2H), 2.18 (s, 4H). 13 C{ 1H}NMR(100MHz, CDCl3)δ-19.8(-SiCH2I),11.7,18.1.

[0091] Example 3: Preparation of exemplary heteroatom-bridged metal-ligand complex catalysts

[0092] [ka]

[0093] To a 250 mL round-bottom flask were added bis(iodomethyl)diisopropylsilane (7.923 g, 20.0 mmol), 2-bromo-4-fluorophenol (11.459 g, 60.0 mmol), K2CO3 (11.056 g, 80.0 mmol), and acetone (50 mL). The reaction mixture was heated to 60 °C for 12 hours and then cooled to room temperature. The reaction mixture was filtered through a short plug of silica gel and rinsed with ether. The solvent was then removed. The residue was purified by column chromatography using ether / hexane (gradient from 0 / 100 to 30 / 70 during elution). 7.428 g of bis((2-bromo-4-fluorophenoxy)methyl)diisopropylsilane (compound (6)) was obtained as a colorless oil (71% yield).

[0094] 1 H NMR (400MHz, CDCl3) δ7.29-7.24(m,2H),6.98(dd,J=6.4,1.7Hz,4H),3.92(s,4H),1.44-1.32(m,2H),1.20(d,J=7.4Hz,12H). 19 F NMR (376MHz, CDCl3)δ-122.63(s,2F).

[0095] [ka]

[0096] To a 40 mL vial, bis((2-bromo-4-fluorophenoxy)methyl)diisopropylsilane (compound (6), 1.045 g, 2.0 mmol), compound (7) (4.164 g, 6.0 mmol), NaCO (1.484 g, 14.0 mmol), and degassed THF (12 mL) were added, all in a glovebox. The vial was capped and removed from the glovebox, and water (5 mL) was added. The stirred solution was purged with nitrogen for 5 minutes to ensure proper degassing. A premixed solution (prepared in the glovebox) of Pd(dba) (0.046 g, 0.08 mmol) and tBuP (0.032 g, 0.16 mmol) in THF (3 mL) was then added in one portion. The reaction was then heated at 70 °C for 18 hours. After cooling to room temperature, the organic layer was transferred to a 100 mL round-bottom flask, and the vial was rinsed with THF (4 mL) and then added to the 100 mL round-bottom flask. MeOH (15 mL) and concentrated HCl (1.0 mL) were added, and the resulting solution was refluxed (80-90 °C) for 2 h. The reaction mixture was concentrated by partial evaporation of the solvent. Water (50 mL) was added, and the product was extracted with ether (80 mL × 2). The combined organic layers were dried over MgSO4 and filtered through a short pad of silica gel. After removing the solvent, the residue was purified by crystallization from ether / ethanol to give 2.42 g of the product (compound (8)) as a white powder (91% yield).

[0097] 1 H NMR(400MHz,CDCl3)δ8.25(brs,4H),7.39(d,J=8.5Hz,4H),7.33(d,J=2.5Hz,2H),7.13(d,J=2.4Hz,2H),6.97(brs,4H),6.77(dd,J=8.7,3.1 Hz,2H),6.30-6.17(m,2H),5.43-5.26(m,2H),5.22(s,2H),3.43-3.06 (m,4H),1.66(s,4H),1.48(s,36H),1.29(s,12H),0.83-0.69(m,32H). 19 F NMR(376MHz, CDCl3)δ-124.11(s,2F). 13C NMR(100MHz,CDCl3)δ157.8,155.5,153.0,147.8,142.8,142.7,139.9,128.9,127.2,126.7,124.0,123.6,123.2,117.62(d,J =23.2Hz),116.0,115.20(d,J=22.8Hz),111.3(d,J=8.8Hz),109.5,56.8,55.8,38.1,34.8,32.4,32.1,31.9,31.6,18.1,9.6.

[0098] [ka]

[0099] In a glovebox, a 100 mL bottle equipped with an oven-dried stir bar was charged with HfCl4 (0.641 g, 2.0 mmol) suspended in anhydrous toluene (60 mL). The bottle was placed in a -30 °C freezer for 1 hour and then removed from the freezer. The reaction mixture was vigorously stirred, and MeMgBr solution (3 M in ether, 2.8 mL, 8.4 mmol) was added. After 13 minutes, the ligand powder (compound (8)) was added as a solid. Stirring was continued overnight at room temperature. The solvent was removed under vacuum to give a dark gray solid. The solid was extracted with anhydrous hexane (90 mL) and then filtered. The filtrate was concentrated to approximately 5–10 mL and then placed in the freezer overnight. The upper clear solution was decanted, and the white solid was dried under vacuum to give 2.53 g of product (compound (9)) (82% yield).

[0100] 1H NMR(400MHz,C6D6)δ8.64-8.60(m,2H),8.42-8.38(m,2H),7.67-7.47(m,8H),7.45-7.39( m,2H),7.26(d,J=2.5Hz,2H),7.07(dd,J=8.9,3.1Hz,3H),6.84-6.75(m,2H),5.27-5.19( m,2H),4.35(d,J=14.1Hz,2H),3.29(d,J=14.1Hz,2H),1.57(d,J=3.5Hz,4H),1.47(s,18H ),1.34-1.19(m,30H),0.80(s,18H),0.58-0.48(m,12H),0.35-0.24(m,2H),-1.08(s,6H). 19 F NMR(376MHz, CDCl3)δ-116.40(m,2F).

[0101] Aspects According to one embodiment, alone or in combination with any other embodiment, Q2X(R 1 )(R 2 ) is provided. 1 and R 2 is a hydrogen atom, (C1 to C 40 ) hydrocarbyl, and optionally R 1 and R 2 are linked to form a ring having 3 to 50 atoms, excluding hydrogen atoms, in the ring. X is Si, Ge, Sn, or Pb. Each Q is independently Ar 1 -Y 1 -R 3 - or Ar 2 -Y 2 -R 4 -R 3 and R 4 is -(CR C 2) m m is 1 or 2; and each R C is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, and —H; Y 1 and Y 2 are independently S, Se, or Te.1 and Ar 2 are independently (C6~C 50 ) aryl. Ar 1 -Y 1 -R 3 - and Ar 2 -Y 2 -R 4 - are not the same.

[0102] According to a second aspect, alone or in combination with any other aspect, Y 1 and Y 2 is Se.

[0103] According to a third aspect, alone or in combination with any other aspect, Y 1 and Y 2 is S.

[0104] According to a fourth aspect, alone or in combination with any other aspect, R 3 and R 4 is -CH2-.

[0105] According to a fifth aspect, alone or in combination with any other aspect, R 3 and R 4 is -CH2CH2-.

[0106] According to a sixth aspect, alone or in combination with any other aspect, Ar 1 and Ar 2 is independently selected from the group consisting of phenyl, 2-methylphenyl, 3-methylphenyl, and 4-methylphenyl.

[0107] According to a seventh aspect, alone or in combination with any other aspect, Ar 1 and Ar 2 is phenyl.

[0108] According to an eighth aspect, alone or in combination with any other aspect, X is Si.

[0109] According to a ninth aspect, alone or in combination with any other aspect, R 1 and R 2 are independently (C1~C 12 ) alkyl.

[0110] According to a tenth aspect, alone or in combination with any other aspect, each Q is selected from the group consisting of Ar 1 -Y 1 -R 3 - and are identical.

[0111] According to an eleventh aspect, alone or in combination with any other aspect, each Q is selected from the group consisting of Ar 1 -Y 1 -R 3 - and R 3 is -CH2- and Y 1 is S and Ar 1 is 4-methylphenyl.

[0112] According to a twelfth aspect, alone or in combination with any other aspect, a heteroatom-bridged precursor, (L 1 )(L 2 )X(R 1 )(R 2 The method for obtaining the compound of formula QX(R1)(R2) (wherein X, Q, R 1 , and R 2 is as defined above) to obtain a heteroatom-bridged precursor. 1 and L 2 independently, -R 3 -Z 1 or -R 4 -Z 1 and each Z 1 are independently selected from Cl, Br, and I.

[0113] According to a thirteenth aspect, alone or in combination with any other aspect, the method comprises reacting a compound of formula (Z 2 )(Z 3 )X(R1 )(R 2 ) compound of formula Q 1 -Li (wherein Q 1 is defined above as Ar 1 -Y 1 -R 3 -), or a single lithium compound having the formula Q 1 -Li (wherein Q 1 is defined above as Ar 1 -Y 1 -R 3 -) and a first lithium compound having formula Q 2 -Li (wherein Q 2 is defined above as Ar 2 -Y 2 -R 4 to obtain a compound of formula Q2X(R1)(R2). 2 and Z 3 is independently selected from Cl, Br, I, and triflate.

[0114] According to a fourteenth aspect, alone or in combination with any other aspect, 2 )(Z 3 )X(R 1 )(R 2 ) with at least a lithium compound to form a compound having the formula (Z 2 )(Z 3 )X(R 1 )(R 2 ) to form a compound having the formula Q 1 -Li, thereby forming a compound of formula (L 1 )(L 2 )X(R 1 )(R 2 ) of the heteroatom-bridged precursor L 1 and L 2 Both -R 3 -Z 1 and this includes being identical.

[0115] According to the fifteenth aspect, alone or in combination with any other aspect, R at all occurrences 3 is -CH2- in this method.

[0116] According to the sixteenth aspect, alone or in combination with any other aspect, R at all occurrences 3 is —CH2CH2— in this method.

[0117] According to a seventeenth aspect, alone or in combination with any other aspect, Z 2 and Z 3 is Cl and Y in all occurrences 1 is S and R at all occurrences 3 is -CH2- and Ar in all occurrences 1 is 4-methylphenyl.

[0118] According to an eighteenth aspect, a compound of formula (Z 2 )(Z 3 )X(R 1 )(R 2 ) with at least one lithium compound to form a compound having the formula (Z 2 )(Z 3 )X(R 1 )(R 2 ) to form a compound having the formula Ar 1 -Y 1 -R 3 -Li and compounds of formula Ar 2 -Y 2 -R 4 -Li, thereby forming a compound of formula (L 1 )(L 2 )X(R 1 )(R 2 ) with heteroatom bridge L 1 and L 2 However, this includes the fact that they are not identical.

[0119] According to a nineteenth aspect, alone or in combination with any other aspect, Z 2 and Z 3 is Cl in this method.

[0120] According to the twentieth aspect, Y at all occurrences, alone or in combination with any other aspect, 1 and Y 2 is S in this method.

[0121] According to the twenty-first aspect, alone or in combination with any other aspect, Ar 1 and Ar 2 is, in this method, independently selected from the group consisting of phenyl, 2-methylphenyl, 3-methylphenyl, and 4-methylphenyl.

[0122] According to the twenty-second aspect, alone or in combination with any other aspect, Ar at all occurrences 1 and Ar 2 is phenyl in this method.

[0123] According to a twenty-third aspect, alone or in combination with any other aspect, in the method, X is Si or Ge.

[0124] According to the 24th aspect, alone or in combination with any other aspect, R 1 and R 2 In this method, independently, (C1 to C 12 ) alkyl.

[0125] According to a 25th aspect, alone or in combination with any other aspect, the method comprises reacting an alkyllithium compound of formula Ar 1 -Y 1 -R 3 -H to form a single lithium compound Q 1 -Li, thereby obtaining a single lithium compound Q 1 or by reacting an alkyllithium compound with a compound of the formula Ar 1 -Y 1 -R 3 -H to form a first lithium compound Q 1and reacting an alkyllithium compound with a compound of the formula Ar 2 -Y 2 -R 4 -H to form a first lithium compound Q 2 obtaining a first lithium compound Q by performing at least one of 1 -Li, a second lithium compound Q 2 -Li, or both.

[0126] According to a twenty-sixth aspect, alone or in combination with any other aspect, at least one alkyl halide is selected from the group consisting of HR 3 -h, HR 4 -h, or a combination thereof, wherein h is a halogen selected from Cl, Br, or I, and the metal halide is Z 1 -Contains Li.

[0127] It will be apparent to those skilled in the art that various modifications can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover modifications and variations of the described embodiments provided that such modifications and variations come within the scope of the appended claims and their equivalents. The present application provides, for example, the following inventions. [1] Equation (3): [ka] (In the formula, R 1 and R 2 is a hydrogen atom, (C 1 ~C 40 ) hydrocarbyl, and optionally R 1 and R 2 are linked to form a ring having 3 to 50 atoms, excluding hydrogen atoms, in the ring; X is Si, Ge, Sn, or Pb; Each Q is independently Ar1 -Y 1 -R 3 - or Ar 2 -Y 2 -R 4 - and R 3 and R 4 is -(CR C 2 ) m m is 1 or 2; and each R C is (C 1 ~C 40 ) hydrocarbyl, (C 1 ~C 40 ) heterohydrocarbyl, and —H; Y 1 and Y 2 are independently S, Se, or Te; Ar 1 and Ar 2 are independently (C 6 ~C 50 ) aryl, Ar 1 -Y 1 -R 3 - and Ar 2 -Y 2 -R 4 - are not identical) compounds. [2] Y 1 and Y 2 is Se. [3] Y 1 and Y 2 is S. [4] R 3 and R 4 is -CH 2 The compound according to any one of the above [1] to [3], wherein [5] R 3 and R 4 is -CH 2 CH 2 The compound according to any one of the above [1] to [3], wherein [6] Ar 1 and Ar 2 is independently selected from the group consisting of phenyl, 2-methylphenyl, 3-methylphenyl, and 4-methylphenyl. [7] Ar 1 and Ar 2 The compound according to any one of the above [1] to [6], wherein is phenyl. [8] The compound according to any one of the above [1] to [7], wherein X is Si. [9] R 1 and R 2 are independently (C 1 ~C 12 The compound according to any one of the above [1] to [8], wherein R is alkyl.

[10] Each Q is Ar 1 -Y 1 -R 3 - and are identical to each other.

[11] Each Q is Ar 1 -Y 1 -R 3 - and R 3 is -CH 2 - and Y 1 is S and Ar 1 is 4-methylphenyl.

[12] A method for obtaining a heteroatom-bridged precursor from a compound according to formula (3), the method comprising: At 90°C to 150°C, at least one alkyl halide, alkali metal halide, and a compound of formula (3):

change

change

[13] The method further includes preparing the compound of formula (3), wherein preparing the compound of formula (3) comprises: At 0°C to 5°C, formula (2)

change

[14] Reacting the compound having formula (2) with at least the lithium compound converts the compound having formula (2) into a compound of formula Q 1 -Li with the single lithium compound, thereby forming L of the heteroatom-bridged precursor having formula (1) 1 and L 2 Both -R 3 -Z 1 The method according to

[13] above, wherein the formula is the same as that of the formula.

[15] R in all occurrences 3 is -CH 2 The method according to

[14] above,

[16] R in all occurrences 3 is -CH 2 CH 2 The method according to

[14] above,

[17] Z in Eq. (2) 2 and Z 3 is Cl, Y in all occurrences 1 is S, R in all occurrences 3 is -CH 2 - and Ar in all occurrences 1 The method according to

[14] above, wherein is 4-methylphenyl.

[18] Reacting the compound having formula (2) with at least one of the lithium compounds converts the compound having formula (2) into a compound of formula Ar 1 -Y 1 -R 3 -Li and compounds of formula Ar 2 -Y 2 -R 4 -Li, thereby forming L of said heteroatom bridge having formula (1) 1 and L 2 are not identical to the method described in

[13] above.

[19] Z in Eq. (2) 2 and Z 3 The method according to any one of the above

[12] to

[18] , wherein is Cl.

[20] Y in all occurrences 1 and Y 2 The method according to any one of the above

[12] to

[19] , wherein is S.

[21] Ar1 and Ar 2 The method according to any one of the above

[12] to

[20] , wherein is independently selected from the group consisting of phenyl, 2-methylphenyl, 3-methylphenyl, and 4-methylphenyl.

[22] Ar in all occurrences 1 and Ar 2 The method according to any one of the above

[12] to

[21] , wherein is phenyl.

[23] The method according to any one of the above

[12] to

[22] , wherein X is Si or Ge. 1 and R 2 are independently (C 1 ~C 12 ) alkyl.

[25] At 0°C to 25°C, an alkyllithium compound having the formula Ar 1 -Y 1 -R 3 -H, to form the single lithium compound Q 1 -Li, thereby obtaining the single lithium compound Q 1 preparing -Li, or At 0°C to 25°C, an alkyllithium compound having the formula Ar 1 -Y 1 -R 3 -H to form the first lithium compound Q 1 -Li, and At 0°C to 25°C, an alkyllithium compound having the formula Ar 2 -Y 2 -R 4 -H to form the first lithium compound Q 2 obtaining the first lithium compound Q 1 -Li, the second lithium compound Q 2 -Li, or both.

[26] The at least one alkyl halide is HR 3 -h, HR 4 -h, or a combination thereof, R 3 and R 4 is as defined in formulas (1) and (3), and h is a halogen selected from Cl, Br, or I; The alkali metal halide is Z 1 -Li, Z 1 The method according to any one of the above

[12] to

[25] , wherein is as defined in formula (1).

Claims

1. 1. A method for obtaining a heteroatom-bridged precursor from a compound according to formula (3), said method comprising: At 90°C to 150°C, at least one alkyl halide, an alkali metal halide, and a compound of formula (3): 【Chemical 1】 (In the formula, R １ and R ２ is a hydrogen atom, (C １ ~C ４０ ) independently selected from hydrocarbyl, and optionally R １ and R ２ are joined to form said ring having 3 to 50 atoms in the ring, excluding hydrogen atoms; X is Si, Ge, Sn, or Pb; Each Q is independently Ar １ -Y １ -R ３ - or Ar ２ -Y ２ -R ４ - and R ３ and R ４ is -(CR Ｃ ２ ) ｍ -, m is 1 or 2, and each R Ｃ is (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, or —H; Y １ and Y ２ are independently S, Se, or Te; Ar １ and Ar ２ are independently ６ ~C ５０ ) aryl, Ar １ -Y １ -R ３ - and Ar ２ -Y ２ -R ４ - are not the same) to form a compound of formula (1): 【Chemistry 2】 (In the formula, R １ , R ２ and X is as defined in formula (3), L １ and L ２ are independently -R ３ -Z １ or -R ４ -Z １ and R ３ and R ４ is as defined in formula (3), and each Z １ is independently selected from Cl, Br, and I.

2. The method further includes preparing the compound of formula (3), wherein preparing the compound of formula (3) comprises: At 0°C to 5°C, the formula (2) 【Chemistry 3】 (In the formula, X, R １ , and R ２ is as defined in formula (3), Z ２ and Z ３ are independently selected from Cl, Br, I, and triflate, Formula Q １ -Li (wherein Q １ is defined as Ar １ -Y １ -R ３ -) or a single lithium compound having the formula Q １ -Li (wherein Q １ is defined as Ar １ -Y １ -R ３ -) and a first lithium compound having formula Q ２ -Li (wherein Q ２ is defined as Ar ２ -Y ２ -R ４ 10. The method of claim 1, comprising reacting a compound of formula (3) with a second lithium compound having a group A, B, C ...

3. Reacting the compound having formula (2) with at least the lithium compound converts the compound having formula (2) into a compound of formula Q １ -Li with the single lithium compound, thereby forming L of the heteroatom-bridged precursor having formula (1) １ and L ２ Both are -R ３ -Z １ and are identical.

4. Z in formula (2) ２ and Z ３ is Cl, Y in all occurrences １ is S, R in all occurrences ３ is -CH ２ - and Ar in all occurrences １ The method of claim 2, wherein is 4-methylphenyl.

5. Reacting the compound having formula (2) with at least one of the lithium compounds converts the compound having formula (2) into a compound of formula Ar １ -Y １ -R ３ -Li and compounds of formula Ar ２ -Y ２ -R ４ with a compound having —Li, thereby forming L of said heteroatom bridge having formula (1) １ and L ２ The method of claim 2 , wherein:

6. At 0°C to 25°C, an alkyllithium compound of the formula Ar １ -Y １ -R ３ -H, to form the single lithium compound Q １ -Li, thereby obtaining the single lithium compound Q １ -Li, or At 0°C to 25°C, an alkyllithium compound of the formula Ar １ -Y １ -R ３ -H-containing compound to form the first lithium compound Q １ -Li, and At 0°C to 25°C, an alkyllithium compound of the formula Ar ２ -Y ２ -R ４ -H-containing compound to form the first lithium compound Q ２ -Li, by performing at least one of the following: obtaining the first lithium compound Q １ -Li, the second lithium compound Q ２ 6. The method of claim 1, further comprising preparing either: -Li, or both.

7. The at least one alkyl halide is HR ３ -h, HR ４ -h, or a combination thereof, R ３ and R ４ is as defined in formulas (1) and (3), and h is a halogen selected from Cl, Br, or I; The alkali metal halide is Z １ -Li, Z １ The method according to any one of claims 1 to 5, wherein is as defined in formula (1).

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