E-selective metathesis catalyst

Abstract

The present invention relates to cationic molybdenum and tungsten complexes containing heterocyclic nitrogen carbene (NHC) and preferably halogen-containing aryloxy ligands. Such catalysts are active in olefin metathesis reactions and can provide E-selectivity.

Description

Technical Field

[0001] This invention relates to cationic molybdenum and tungsten complexes containing N-heterocyclic carbene (NHC) and preferably halogenated aryloxy ligands. Such catalysts are active in olefin metathesis reactions and can provide… E -Selectivity. Background Technology

[0002] Most olefin metathesis catalysts, such as molybdenum-based, tungsten-based, and ruthenium-based catalysts, are known to provide a mixture of cis / trans isomers when forming new olefins with internal double bonds. Monoaryloxypyrrolidine (MAP) type molybdenum-based and tungsten-based Schrock alkylene compounds containing large aryl groups were among the earliest catalysts to catalyze cis / trans isomerization. Z The catalyst for the formation of the C=C double bond, and the first ruthenium group Z The selective catalyst was introduced by Grubbs (Schrock and Grubbs, 2005 Nobel laureates). In the metathesis reaction of terminal double bonds, the ruthenium-dithiolate complex also exhibited high selectivity even at relatively high catalyst loadings. Z Selectivity. In cross-metathesis reactions of internal alkenes, this complex also provides stereoregulation.

[0003] MJ Benedikter et al., “Group 6 metal alkylidene and alkylidyne N-heterocyclic carbene complexes for olefin and alkyne metathesis”, Coordination Chemistry Reviews 415 (2020) 213315, disclosed in Table 14, which defines some aryloxy-substituted cationic NHC molybdenum catalysts that exhibited ring-opening cross metathesis (ROCM) of 2,3-disubstituted norbornene using various substrates. E -Selectivity, while similar catalysts exhibit Z -Selectivity.

[0004] The authors of this publication, in Figures 22 and 24 and in conjunction with Table 14, suggest that the steric hindrance of the imine ligand in the metal cyclobutane formed by the catalyst and the substrate, and / or the chelating effect of the substrate and the catalyst, may affect the metathesis products. E / Z The proportion has an impact.

[0005] WO 2015 / 162245 discloses N-heterocyclic carbene complexes of metal iminoalkylene and metal oxoalkylene and their use as catalysts in olefin metathesis reactions. As broadly defined therein, the catalysts have formulas I to IV: , According to the definition, A 1 Representing NR 2 or PR 2 A 2 Represents CR 2 R 2' NR 2 PR 2 O or S, A 3 Represents N or P, and C represents a carbene carbon atom. Ring B is an unsubstituted, monosubstituted, or polysubstituted 5- to 7-membered ring. Substituent R 2 and R 2' Especially representing linear or branched C1-C 10 Alkyl group, and if A 1 and A 2 All represent NR 2 or PR 2 If they are the same or different, then M in formulas I, II, III or IV represents Cr, Mo or W, and X in formulas I to IV represents Cr, Mo or W. 1 or X 2 Same or different, and especially representing C1-C 18 Carboxylates and C1-C 18 Alkoxides, Y especially oxygen or sulfur, Z especially linear or branched C1-C 10 Alkylene oxide, and R in formulas I to IV 1 and R 1' Especially aliphatic or aromatic groups.

[0006] For example, from I. Reim et al.'s "Towards" EAs further discussed in "Selective Olefin Metathesis: Computational Design and Experimental Realization of Ruthenium Thio-Indolate Catalysts", Topics in Catalysis, Volume 65, pages 448–461 (2022), E-olefins with substituents arranged in trans configuration on the double bonds are an important structural feature of a wide range of molecular entities, from antibiotics and anticancer drugs to sophisticated polymers. This reference points out that, to date, the metathesis synthesis of E-olefin products has only been achieved through "stereoretaining" catalysts (such as ruthenium dithiocatechin catalysts), which can convert stereochemically defined E-olefin substrates into E-type products. The application of stereoretaining metathesis reactions is limited by the cost and availability of the required isomer-pure starting materials.

[0007] Despite advancements in existing technologies, the production of E-olefin products remains a highly attractive intellectual and economic challenge.

[0008] Purpose of the invention The object of this invention is to provide complexes by which E-selective formation of olefins can be achieved in olefin metathesis reactions, while taking into account the industrial requirements for the application of such catalysts. Industrially feasible and economical processes require the use of highly active catalysts, thereby allowing for low catalyst loadings, typically below 100 ppm or 0.01 mol%. Invention Overview The above objective is achieved by the compound defined in independent claim 1. Contrary to the teachings of the prior art, the inventors have discovered that cationic molybdenum and tungsten complexes with nitrogen-containing heterocyclic carbenes, particularly halogen-containing aryloxy substituents, exhibit favorable E-selectivity in olefin metathesis reactions. In a preferred embodiment, the halogen-containing aryloxy substituent is a chlorinated aryloxy substituent.

[0010] The present invention also relates to molybdenum and tungsten complexes as defined in independent claim 2.

[0011] The present invention also discloses intermediates for preparing the compounds of the present invention according to claims 1 and 2. Advantageously, these compounds, as defined herein, can also exhibit catalytic activity in metathesis reactions, wherein the metathesis reactions are E-selective. The claims that are subordinate to the independent claims represent their preferred embodiments. Invention Details In one aspect, the present invention relates to compounds of formula I: , in: M is Mo or W; NHC is a nitrogen-containing heterocyclic carbene, which is bonded to M through its carbene carbon atom; X is =NR 1 ; Y represents an alkylene or arylene group = CR 2 R 3 ; Z represents an aryloxy residue -OR 4 ; L is a neutral ligand; n is 0 or 1; A is a noncoordinate anion; in: R 1 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; R 2 and R 3 Independently, each -C can be arbitrarily replaced. 1-10 Alkyl or -C 6-14 Aryl, or -H, where R 2 and R 3 Not both H; R 4 It is a phenyl group or a phenyl group substituted with at least one halogen atom; The prerequisite is that the compound of formula I is not a compound of any of the following formulas known in the prior art: .

[0013] In one implementation, the compound of formula I is not a compound of the following formula. [M(NHC)(X)(Y)(-OC6F5)(L) n A, Among them, M, NHC, X, Y, L, n, and A have the meanings defined above.

[0014] In another embodiment, in the compound of formula I, R 4 It is a phenyl or a phenyl substituted with at least one halogen atom, wherein the halogen atom is selected from chlorine and bromine.

[0015] In another aspect, the present invention relates to compounds of formula II, , in: M is either Mo or W; Mo is preferred. NHC is a nitrogen-containing heterocyclic carbene, which coordinates with M through its carbene carbon atom; X is =NR 1 ; Y represents an alkylene or arylene group = CR 2 R 3 ; Z represents an alkoxy or aryloxy residue -OR 4 ; L is a neutral ligand; n is 0 or 1; A is a noncoordinate anion; in: R 1 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; R 2 and R 3 Independently, each -C can be arbitrarily replaced. 1-10 Alkyl or -C 6-14 Aryl, or -H, where R 2 and R 3 Not both H; R 4 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; The prerequisite is that the following compounds not included in the prior art are not included: , , , , , , , , , , , , , , .

[0016] In one embodiment, compounds of formula II exclude compounds of formula I.

[0017] In another aspect, compounds of formula III were disclosed. , in: M is Mo or W; NHC is a nitrogen-containing heterocyclic carbene, which coordinates with M through its carbene carbon atom; X is =NR 1 ; Y represents an alkylene or arylene group = CR 2 R 3 ; Z stands for trifluoromethanesulfonate (trifluoromethanesulfonate, TfO) - CF3SO3 - ); or a halide selected from Cl- or Br-; or -OR 4 , where R 4 To arbitrarily replace C 1-10 Alkyl or C 6-14 Aryl; L is a neutral ligand or an anionic ligand, wherein the anionic ligand is trifluoromethanesulfonate; or is selected from Cl. - or Br - halides; n is 0 or 1; A is a noncoordinate anion; m is 0 or 1; where: R 1 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; R 2 and R 3 Independently, each -C can be arbitrarily replaced. 1-10 Alkyl or -C 6-14 Aryl, or -H, where R 2 and R 3 They are not both H.

[0018] In a preferred embodiment, in the compound of formula III, (i) Z and L are TfO or Br respectively, and n is 1 and m is 0; or (ii) Z is OR 4 And L is TfO or Br, and n is 1 and m is 0; or (iii) Z is either TfO or Br, L is a neutral ligand, n is 0 or 1 and m is 1.

[0019] In one embodiment, the compound of formula III is itself active in a metathesis reaction, wherein the metathesis reaction is E-selective. This is particularly applicable to cationic compounds (iii) also defined according to the invention.

[0020] In another embodiment, the compound of formula III is used as an intermediate or starting material for the synthesis of compounds of formula I and formula II.

[0021] In one embodiment, the NHC in compounds of formulas I, II, and III is selected from the group consisting of: Nitrogen-containing heterocyclic carbene containing formula 6 , Among them, R is defined in Equation 6 7 and R 8 Each can be independently H, unbranched or branched C. 1-20 Alkyl, C 5-9 Cycloalkyl or phenyl, wherein the phenyl group is optionally composed of up to three independently selected from unbranched or branched C4 groups. 1-6 Alkyl, C 1-6 Alkoxy or halogen groups are substituted, and Wherein, the chemical bonds, indicated by wavy lines, are respectively connected to the optionally substituted alkenyl or alkylene groups, wherein the carbene carbon atom, the two nitrogen atoms, and the optionally substituted alkenyl or alkylene groups form a ring; or Nitrogen-containing heterocyclic carbene, including the part of formula 7 , Wherein, Ar as defined in Formula 7 is an aryl group, preferably optionally substituted with one or more phenyl groups selected from the group consisting of: C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryl, C6-C 14 aryloxy or halogen; and The chemical bonds, indicated by wavy lines, are respectively connected to the optionally substituted alkenyl or alkylene groups, wherein the carbon atom, carbene carbon atom, nitrogen atom, and optionally substituted alkenyl or alkylene groups form a ring, which may optionally be bridged by the alkylene groups.

[0022] In a preferred embodiment, the NHC is selected from the group consisting of: Wherein, the carbene in formula 6 is one of formulas 6a, 6b, 6c or 6d: , , or , Among them, R 9 and R 10 Each is independently H, unbranched or branched C. 1-20 Alkyl or phenyl, wherein the phenyl group is optionally composed of up to three C groups independently selected from unbranched or branched C groups. 1-6 Alkyl, C 1-6 Alkoxy or halogen group substitution; or R 9and R 10 It combines with the carbon atoms it is attached to to form a 3- to 8-membered carbon ring, preferably an aromatic ring, more preferably C6H4; Y and Y' are halogens; More preferably, wherein NHC is formula 6a or formula 6b, and more preferably, R as defined in formula 6a or formula 6b 9 and R 10 H, and R as defined in equation 6a or 6b. 7 and R 8 It is trimethylbenzyl or 2,6-diisopropylphenyl; or Where NHC is the formula (n=1 to 8).

[0023] In one implementation, the carbene of Formula 7 is a carbene of either Formula 7a or Formula 7b: , In Equation 7a, each R is independently hydrogen, C1-C 12 Alkyl, C3-C 12 cycloalkyl, C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryloxy or halogen atom substitution; and wherein the two R atoms separated by the C-CR2-C portion can combine to form a ring system; or Carbene of type 7b , In Equation 7b, each R is independently hydrogen, C1-C 12 Alkyl, C3-C 12 cycloalkyl, C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryloxy or halogen atom substitution; wherein n is 1, 2 or 3; preferably, wherein each R in formula 7b is independently hydrogen, C1-C 12Alkyl or C3-C 12 Cycloalkyl.

[0024] In a preferred embodiment, the ligand of formula 7a is formula 7a'. , Among them, R in equation 7a' 12 R 13 R 14 and R 15 Each independently is hydrogen, C1-C 12 Alkyl, C3-C 12 cycloalkyl, C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryloxy or halogen atom substitution; and wherein, R 12 and / or R 13 Can be used with R 14 and / or R 15 Combining to form a ring system; or The ligand of formula 7b is formula 7b': , Among them, R in equation 7b' 16 R 17 and R 18 Each is independently a hydrogen atom or a C1-C atom. 12 Alkyl, or C3-C 12 cycloalkyl, or C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryloxy or halogen atom substitution, preferably, wherein R in formula 7b' is substituted. 16 R 17 and R 18 Each independently constitutes H, C1-C 12 Alkyl or C3-C 12 Cycloalkyl.

[0025] In another preferred embodiment, NHC in Formula 7 is the carbene of Formula 7c. , In Equation 7c, m is an integer from 0 to 4, and each R y Independently possessing C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryl, C6-C 14 The meaning of aryloxy or halogen; for example, carbene of formula 7c'. , Or a 7d carbene , In Equation 7d, m is an integer from 0 to 4, and each R y Independently possessing C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryl, C6-C 14 The meaning of aryloxy or halogen; for example, carbene of formula 7d'. , Or a carbene of type 7e , Or a carbene of formula 7f , Or a carbene of formula 7g or 7h , Or a carbene of type 7i , Or a 7k carbene , Furthermore, each R in formulas 7c to 7i is independently hydrogen or C1-C. 12 Alkyl, or C3-C 12 cycloalkyl, or C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14Aryloxy or halogen atom substitution; preferably, each R in formulas 7c to 7i is hydrogen, C1-C1, or C2-C2. 12 Alkyl or C3-C 12 Cycloalkyl.

[0026] In a preferred embodiment, the NHC is selected from the following NHCs: , (IMesH2 is also known as SIMes).

[0027] In one implementation, for compounds of formulas I and III, targeting R 1 R 2 and R 3 For any of these, the term "optionally substituted" means that the substituent is independently chosen from C. 1-5 Alkyl, C 1-5 Alkoxy, halogen, nitro, N(C) 1-5 Alkyl)2、-NH-C(O)C 1-5 Alkyl, phenyl, phenoxy, wherein the phenyl group in phenyl and phenoxy groups can be further converted into C 1-5 Alkyl, C 1-5 Alkoxy, halogen, nitro, N(C) 1-5 Alkyl)2、-NH-C(O)C 1-5 One or more of the alkyl groups are substituted.

[0028] In one implementation, for compounds of formula II, targeting R 1 R 2 R 3 and R 4 For any of these, the term "optionally substituted" means that the substituent is independently selected from C. 1-5 Alkyl, C 1-5 Alkoxy, halogen, nitro, N(C) 1-5 Alkyl)2、-NH-C(O)C 1-5 Alkyl, phenyl, phenoxy, wherein the phenyl group in phenyl and phenoxy groups can be further converted into C 1-5 Alkyl, C 1-5 Alkoxy, halogen, nitro, N(C) 1-5 Alkyl)2、-NH-C(O)C 1-5 One or more alkyl groups are substituted.

[0029] In one embodiment, in the compounds according to formulas I, II, and III, R 2 and R 3 One of them is hydrogen, and R 2 and R 3The other is -C(CH3)3 or -C(CH3)2C6H5. According to the present invention, R 2 and R 3 They are not both H.

[0030] According to the present invention, R in compound I 4 Selected from phenyl or phenyl with at least one halogen atom substituted.

[0031] In one implementation, for compound I, R 4 It is C6H5.

[0032] In another embodiment, R in compound I 4 It is a phenyl group that has been substituted with at least one halogen atom.

[0033] In one implementation, the halogen is selected from F, Cl, and Br.

[0034] In one embodiment, the phenyl group contains only F as at least one halogen.

[0035] In a preferred embodiment, the phenyl group contains only Cl as at least one halogen.

[0036] In yet another preferred embodiment, the phenyl group contains only Br as at least one halogen.

[0037] In a preferred embodiment, the phenyl group contains F and Cl as at least one halogen.

[0038] In another preferred embodiment, the phenyl group contains F and Br as at least one halogen.

[0039] In another preferred embodiment, the phenyl group contains Cl and Br as at least one halogen.

[0040] In another preferred embodiment, the phenyl group contains F, Cl, and Br as at least one halogen.

[0041] In one implementation, for compounds of formula I, R 4 It is selected from monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl or pentafluorophenyl.

[0042] In a preferred embodiment, the phenyl group contains at least one halogen, and the halogen is Cl. In one embodiment, R 4 It is selected from monochlorophenyl, dichlorophenyl, trichlorophenyl, tetrachlorophenyl or pentachlorophenyl.

[0043] In a preferred embodiment, R 4It is selected from 2-chlorophenyl; 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl; 3-chlorophenyl; 3,4-dichlorophenyl, 3,5-dichlorophenyl; 4-chlorophenyl; 2,3,4-trichlorophenyl, 2,3,5-trichlorophenyl and 2,3,6-trichlorophenyl.

[0044] In another implementation, R 4 It is selected from monobromophenyl, dibromophenyl, tribromophenyl, tetrabromophenyl, or pentabromophenyl.

[0045] The term "neutral ligand" (L) used in compounds according to formulas I, II and III covers a neutral molecule that donates an electron pair to the central metal of the complex.

[0046] In one embodiment, the neutral ligand L is selected from ethers, phosphine, nitriles or pyridine, dimethyl sulfoxide, acetone and dimethylformamide.

[0047] In a preferred embodiment, the nitrile is selected from acetonitrile (ACN), tert-butylnitrile (trimethylacetonitrile, neopentanonitrile, PivCN) and benzonitrile.

[0048] In this document, the term "anionic ligand" as used for compounds of formula III encompasses a negatively charged ion that donates an electron pair to the central metal of the complex. In the context of this invention, anionic ligands are trifluoromethanesulfonates and halides, such as chlorides and bromides.

[0049] As used herein, the term "coordination anion" encompasses a negatively charged ion that interacts strongly with a cation. For example, in some embodiments, anionic ligands may also be considered coordination anions.

[0050] In this article, the term “noncoordinate anion” (A) used for compounds according to formulas I, II and III covers negatively charged ions that weakly interact with cations.

[0051] In one implementation, the noncoordinate anion is selected from perchlorate [ClO4]. - Tetrafluoroborate [BF4] - hexafluorophosphate [PF6] - SbF6 (hexafluoroantimonate) - Tetraphenylborate [BPh4] - Tetra(trifluoromethyl)borate [B(CF3)4] - Tetra(pentafluorophenyl)borate [B(C6F5)4] - Tetra(3,5-bis(trifluoromethyl)phenyl)borate[B{(3,5-di-CF3)C6H3}4] -And tetra(nonafluorotert-butoxy)aluminate [Al{OC(CF3)3}4] - A group that is formed.

[0052] Therefore, such as [M(NHC)(X)(Y)(Z)(L)] n Formulas like [M(NHC)(X)(Y)(Z)(L)], where A is a non-coordinated anion, must be interpreted as [M(NHC)(X)(Y)(Z)(L)]. n ] + A - The meaning of .

[0053] According to the present invention, certain compounds known from the Benedikter references mentioned in the background section or WO 2015 / 162245 are excluded from the compounds according to Formula I and Formula II, respectively.

[0054] In another aspect, the present invention relates to the use of compounds known from the Benedikter references mentioned in the background section and excluded from the compounds of Formula I (i.e., compounds of the following formula) for E-selective olefin metathesis reactions: , , , , ,or .

[0055] In another aspect, the present invention relates to the use of compounds known from the Benedikter references mentioned in the background section and excluded from the compounds of formula II (i.e., compounds of the following formula) for E-selective olefin metathesis reactions: , , , , , , , ,and .

[0056] The compounds according to the present invention can be used in all types of olefin metathesis reactions.

[0057] In one embodiment, the compound according to the invention undergoes a cross metathesis reaction (CM), including a self metathesis reaction [(homologous) cross metathesis reaction (HCM)].

[0058] In another embodiment, the compound according to the invention undergoes a closed-ring metathesis reaction (RCM).

[0059] In another embodiment, the compound according to the invention undergoes a ring-opening metathesis reaction (ROM).

[0060] In another embodiment, the compound according to the invention undergoes a ring-opening metathesis polymerization (ROMP) reaction.

[0061] In another embodiment, the compound according to the invention undergoes an acyclic diene metathesis reaction (ADMET).

[0062] Preferably, the olefins prepared in the metathesis reaction are mainly in the E configuration, unless they are spatially impossible to form, such as forming small rings in the RCM reaction.

[0063] The term "majorly E-configuration" means that at least 75% of the olefins formed are E-olefins and at most 25% are Z-olefins.

[0064] In another embodiment, at least 80% is E-olefins and at most 20% is Z-olefins.

[0065] In another embodiment, at least 85% is E-olefins and at most 15% is Z-olefins.

[0066] In another embodiment, at least 90% is E-olefins and at most 10% is Z-olefins.

[0067] In another embodiment, at least 95% is E-olefins and at most 5% is Z-olefins.

[0068] In another aspect, the present invention relates to a method for carrying out a metathesis reaction, comprising reacting a compound of formula I or II with one or more olefins.

[0069] In another aspect, the present invention relates to a method for carrying out a metathesis reaction, comprising: React the compound of formula III with one or more olefins. , in: M is Mo or W; NHC is a nitrogen-containing heterocyclic carbene, which is bonded to M through its carbene carbon atom; X is =NR 1 ; Y represents an alkylene or arylene group = CR 2 R 3 ; Z represents trifluoromethanesulfonate (TfO); or a halide selected from Cl- or Br-; or -OR. 4 , where R 4 To arbitrarily replace C 1-10 Alkyl or C 6-14 Aryl; L is a neutral ligand or an anionic ligand, wherein the anionic ligand is trifluoromethanesulfonate; or is selected from Cl. - or Br - halides; n is 0 or 1; A is a noncoordinate anion; m is 0 or 1; in: R 1 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; R 2 and R 3 Independently, each -C can be arbitrarily replaced. 1-10 Alkyl or -C 6-14 Aryl, or -H, where R 2 and R 3 Not both H; In the compounds of formula III: (iii) Z is either TfO or Br, L is a neutral ligand, n is 0 or 1 and m is 1.

[0070] In one embodiment, the metathesis reaction is a metathesis reaction between an unsaturated fatty acid ester and ethylene.

[0071] Example According to the present invention, compounds of formula I, II or III are prepared by known methods, for example, those disclosed in Benedikter references or WO 2015 / 162245, as mentioned in the background section and outlined below.

[0072] A general scheme for synthesizing cationic molybdenum NHC aryloxy complexes according to Formula I or II (DCM = dichloromethane):

[0073] A general scheme for synthesizing cationic tungsten NHC aryloxy complexes according to Formula I or Formula II:

[0074] A general scheme for synthesizing molybdenum NHC monoaryloxy monotrifluoromethanesulfonate complexes according to formula II:

[0075] Table 1 lists Schrock-type carbenes. These catalysts are used for comparison.

[0076] Table 1 , (The term “bitetO” covers a ligand derived from 5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2-ol, which binds to M in its alkoxide form by abstracting a proton from the phenolic hydroxyl group; Ph represents phenyl).

[0077] Tables 2 and 3 list the Mo-NHC bis(trifluoromethanesulfonate), W-NHC dibromide, Mo-aryloxytrifluoromethanesulfonate, and cationic Mo and W-trifluoromethanesulfonate and bromide prepared according to formula III (X359 to X963; Y = CHCMe2C6H5).

[0078] Table 2 , (SIMes refers to 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole-2-ylene; IMes refers to 1,3-bis(2,4,6-trimethylphenyl)-imidazole-2-ylene).

[0079] Table 3 , (BArF used in this article refers to tetrakis(3,5-bis-(trifluoromethyl)phenyl)borate [B{(3,5-di-CF3)C6H3}4]) - ).

[0080] Table 4 lists the cationic Mo- and W-NHCs prepared according to Formula I (X945 to X968; X979 to X954) and Formula II (X973).

[0081] Table 4 , (HMTO = hexamethyl terphenolate = 2,5-dimesitylphenolate; ACN = acetonitrile; PivCN = pivaloylnitrile; Ad = 1-adamantyl).

[0082] The catalytic activity and stereoselectivity of the prepared molybdenum and tungsten NHC complexes were tested in cross metathesis and ethylene hydrolysis reactions and compared with selected MAP catalysts.

[0083] Specific examples All reactions were carried out in a nitrogen-filled glove box using oven-dried glassware. Toluene and pentane were distilled using sodium / benzophenone. Dichloromethane was distilled using CaH2. All solvents were further dried by storage on molecular sieves (4 Å).

[0084] X359 Synthesis

[0085] 39.56 g of bis(trifluoromethanesulfonate) (Mo(2,6-Me2PhN)(CHCMe2Ph)(TfO)2xDME) was dissolved in toluene (700 mL). The clear, brownish-orange solution was cooled to -20 °C. 16.373 g of IMes was dissolved in toluene (150 mL) to give a clear, colorless solution. The cooled IMes toluene solution was slowly added. The reaction mixture darkened in color. A yellow solid precipitated after 10 minutes. The reaction mixture was stirred at -20 °C for 1 hour, then slowly heated to 25 °C and stirred for another 3 hours. The precipitated yellow solid was filtered, washed with cold toluene (3 × 30 mL) and pentane (3 × 30 mL), and then dried under a nitrogen stream. The yield was 45 g (88%).

[0086] 1 ¹H NMR (300MHz, CD₂Cl₂, 296K) δ = 13.18 (s, Mo=CH⁻, 1H), 7.23–7.03 (m, Ar-H, 8H), 7.96 (broad, Mes-H, 2H), 7.96 (broad, Mes-H, 2H), 6.56 (broad s, imidazole CH, 2H), 2.60 (broad, Mes-Me, 3H), 2.25 (s, Ar-H, 3H), 2.13 (s, Ar-H, 3H), 1.98 (s, CHCMe₂Ph, 3H), 1.96 (s, Ar-H, 3H), 1.88 (broad, Mes-Me, 3H), 1.30 (s, CHCMe₂Ph, 3H) ppm. 19 F NMR (282MHz, CD2Cl2) δ = -74.94 (width s, OTf, 3F), -76.52 (width s, OTf, 3F) ppm.

[0087] X930 Synthesis

[0088] Sodium tetrakis(3,5-bis-(trifluoromethyl)phenyl)borate (6.20 g) was added in portions to a solution of X359 (6.65 g) in DCM (35 mL). The reaction mixture was stirred overnight at 25 °C. The resulting orange-yellow suspension was filtered through diatomaceous earth, and the filter was washed with DCM. The mother liquor was evaporated to dryness, and the resulting light brown foam was ground in pentane. After filtration and drying, 11 g (94%) of yellow powder was obtained.

[0089] 1 H NMR (300MHz, CD2Cl2, 296K) δ = 13.05 (s, Mo=CH-, 1H), 7.72 (m, B-Ar-H( Adjacent ), 8H), 7.56 (s, B-Ar-H( Opposition ), 4H), 7.46 (s, imidazole CH, 2H), 7.14-7.00 (m, Ar-H, 5H), 6.97 (t, -CMe2Ph( Interposition ), 2H), 6.92 (wide d, Ar-H, 2H), 6.85 (wide s, Ar-H, 2H), 6.76 (t, Ar-H, 1H), 2.33 (s, Me, 6H), 2.08 (s, Me, 6H), 2.06 (wide, Me, 3H), 1.90 (wide s, Me, 6H), 1.84 (wide, Me, 3H), 1.14 (s, CHCMe2Ph, 3H), 1.00 (s, CHCMe2Ph, 3H) ppm. 19 F NMR (282MHz, CD2Cl2) δ = -62.88 (s, Ar-CF3, 24F), -73.58 (s, OTf,2F) ppm.

[0090] X942 Synthesis

[0091] Solid lithium phenolate was added in portions to a cold solution of X359 (8.55 g) in DCM (50 mL) at -35 °C. The reaction mixture was heated and stirred at 25 °C for 3 hours. The orange-yellow suspension was filtered through diatomaceous earth, and the filter was washed with DCM. The mother liquor was evaporated to dryness, and the resulting light brown foam was ground with pentane. After filtration and drying, 7.3 g (91%) of yellow powder was obtained.

[0092] 1 H NMR (300MHz, C6D 6,323K) δ = Two isomers (a and b), 14.88 a (s, Mo=CH-, 1H), 13.92 b (s, Mo=CH-, 1H), 7.45 a+b (m, Ar-H, 2H), 7.27 a (dd, Ar-H, 1H), 7.21 b (m, Ar-H, 1H), 7.19 a (m, Ar-H, 2H), 7.09-7.02 a+b (m, Ar-H, 2H), 6.93-6.73 (m, Ar-H,3H), 6.65 a+b (m, Ar-H, 1H), 6.53 a+b (m, Ar-H, 1H), 6.44 a+b (m, Ar-H, 1H), 6.41 a+b (m,Ar-H, 2H), 6.30 a (m, Ar-H, 1H), 6.04 b (s, imidazole CH, 2H), 5.95 a (s, imidazole CH, 2H), 2.74 b (width s, Me, 3H), 2.46 a (width s, Me, 3H), 2.25 a (width s, Me, 3H), 2.19 b (width s, Me, 3H), 1.99 b (s, Me, 6H), 1.95 a (s, Me, 3H), 1.91 a (s, Me, 3H), 1.80 b (s, Me, 3H), 1.71 a (s, Me, 3H), 1.69 b (s, Me, 3H), 1.56 a (s, Me, 3H) ppm. 19 F NMR (282MHz, C6D6, 323K) δ = -77.49 b (width s, OTf, 3F), -77.58 a (width s, OTf, 3F) ppm.

[0093] X948 Synthesis

[0094] Solid lithium 2,6-dichlorophenol (1.11 g) was added in portions to a cold solution of X930 (11.00 g) in 50 mL of DCM at -35 °C. The reaction mixture was heated and stirred at 25 °C for 3 hours. The orange-yellow suspension was filtered through diatomaceous earth, and the filter was washed with DCM. The mother liquor was evaporated to dryness, and the resulting light brown foam was ground with pentane. After filtration and drying, 10.46 g (94%) of yellow powder was obtained.

[0095] 1 H NMR (300MHz, CD2Cl 2, 296K) δ = 12.92 (s, Mo=CH-, 1H), 7.73 (m, B-Ar-H( Adjacent ), 8H), 7.56 (s, B-Ar-H( Opposition ), 4H), 7.30 (d, Ar-H, 2H), 7.21-7.10 (m, Ar-H, 4H), 6.99-6.90 (m, Ar-H, 6H), 6.84 (t, Ar-H, 1H), 6.61 (s, imidazole CH, 2H), 2.15 (wide s, Me, 6H), 2.13 (wide s, Me, 3H), 2.12 (wide s, Me, 3H), 2.10 (wide, Me, 3H), 1.88 (s, CHCMe2Ph, 3H), 1.35 (s, CHCMe2Ph, 3H) ppm. 19 F NMR (282MHz, CD2Cl2, 296K) δ = -62.87 (s, B-Ar-CF3) ppm.

[0096] Synthesis of W(3,5-Me2PhN)(CHCMe2Ph)(Br)2xDME

[0097] The corresponding bis(trifluoromethanesulfonate) (12.00 g) and KBr (10.4 g, 6 equivalents) were mixed in DCM / DME (110 mL / 12 mL), and the reaction mixture was stirred at 25 °C for 4 days. The reaction mixture was filtered, the solvent was evaporated, and a brick-red solid was given. This solid was suspended in pentane, filtered, and dried. 9.12 g (91%) of red powder was obtained.

[0098] 1H NMR (300MHz, CD2Cl 2, 296K) δ = 10.58 (s, W=CH-, 1H), 7.78 (d, Ph-H( Adjacent ), 2H), 7.43 (s, N-Ar-H( Adjacent ), 2H), 7.30 (t, Ph-H( Interposition ), 2H), 7.06 (t,Ph-H( Opposition ), 1H), 6.54 (s, N-Ar-H (para), 1H), 3.24 (s, -OMe, 6H), 3.14 (wide s, -O-CH2-CH2-O-, 4H), 1.94 (wide s, Me, 6H), 1.92 (wide s, Me, 6H) ppm.

[0099] X959 Synthesis

[0100] (W(3,5-Me2PhN)(CHCMe2Ph)(Br)2xDME (9.1 g) was dissolved in toluene (350 mL). The clear, brownish-orange solution was cooled to -20 °C. IMes (4.04 g) was dissolved in toluene (50 mL) to give a clear, colorless solution. The cooled IMes toluene solution was slowly added. The reaction mixture was stirred at -20 °C for 1 hour, then slowly heated to 20 °C and stirred overnight at 25 °C. The reaction mixture was concentrated by evaporating half of the solvent. The precipitated yellow solid was filtered, washed with cold toluene and pentane, and then dried under a nitrogen stream. 8.92 g (74%) was given.

[0101] 1 H NMR (300MHz, CD2Cl 2, 296K) δ = 9.64 (s, W=CH-, 1H), 7.21 (m, Ar-H, 5H), 7.09 (s, Ar-H, 2H), 6.79 (wide s, Ar-H, 1H), 6.54 (overlapping wide signal, 6H), 2.25 (s, N-ArMe2, 6H), 2.13-2.03 (wide signal, Mes-Me, 18H), 1.64 (s, CHCMe2Ph, 3H), 1.47 (s, CHCMe2Ph, 3H) ppm.

[0102] X963 Synthesis

[0103] To a suspension of sodium tetra(3,5-bis-(trifluoromethyl)phenyl)borate (8.76 g) in DCM (16 mL), trimethylacetonitrile (PivCN, 1.1 mL) was added, followed by a solution of X959 (8.90 g) in 50 mL of DCM. The reaction mixture was stirred overnight at 25 °C and then filtered through a diatomaceous earth mat. The mother liquor was evaporated to dryness, and the resulting brown foam was ground in pentane. After filtration and drying, 16.4 g (94%) of yellow powder was obtained.

[0104] 1 H NMR (300MHz, CD2Cl 2, 296K) δ = 10.35 (s, W=CH-, 1H), 7.72 (m, B-Ar-H( Adjacent ), 7.56 (s, B-Ar-H( Opposition ), 7.32-7.24 (m, -Ph ( Interposition and Opposition ), 3H), 7.22 (s,N-Ar-H( Adjacent ), 2H), 7.15 (m, -Ph ( Adjacent ), 2H), 6.87 (width s, N-Ar-H( Opposition ), 1H), 6.62 (width s, Mes-Ar-H( Interposition ), 4H), 6.36 (wide s, imidazole CH, 2H), 2.25 (s, Mes-Me, 6H), 2.12 (s, Mes-Me, 12H), 1.96 (s, Mes-Me, 6H), 1.63 (s, CHCMe2Ph, 3H), 1.58 (s, CHCMe2Ph, 3H), 1.15 (s, N≡C- t Bu, 9H) ppm. 19 F NMR (282MHz, CD2Cl2, 296K) δ = -62.9 ppm.

[0105] X965 Synthesis

[0106] Solid lithium 2,6-dichlorophenol (574 mg) was added in portions to a cold solution of X963 (6.00 g) in 50 mL of DCM at -35 °C. The reaction mixture was heated and stirred at 25 °C for 3 hours. The orange-yellow suspension was filtered through diatomaceous earth, and the filter was washed with DCM. The mother liquor was evaporated to dryness, and the resulting light brown foam was ground in pentane. After filtration and drying, 5.85 g (93%) of yellow powder was obtained.

[0107] 1 H NMR (300MHz, CD2Cl 2, 296K) δ = 11.96 (s, W=CH-, 1H), 7.72 (m, B-Ar-H( Adjacent ), 7.56 (s, B-Ar-H( Opposition ), 7.34-7.14 (m, Ar-H, 7H), 7.21 (s, Ar-H, 2H), 6.79 (t, OPhCl2-H( Opposition ), 1H), 6.75 (wide s, Ar-H, 3H), 6.63 (wide s, Ar-H, 2H), 6.36 (wide s, imidazole CH, 2H), 2.22 (s, Me, 6H), 2.16 (s, Me, 6H), 1.99 (s, Me, 6H), 1.87 (s, Me, 6H), 1.74 (s, Me, 3H), 1.69 (s, Me, 3H), 0.73 (s, N≡C- t Bu,9H) ppm. 19 F NMR (282MHz, CD2Cl2, 296K) δ = -62.9 ppm.

[0108] Synthesis of Mo(Me₂PhN)(CHCMe₂Ph)(IMes)(2,6Cl₂PhO)(OTf) X₁₀₄₃

[0109] Solid lithium 2,6-dichlorophenol (267 mg) was added in portions to a cold solution of X359 (1.5 g) in DCM (15 mL) at -10 °C. The reaction mixture was heated and stirred at 25 °C for 3 hours. The orange-yellow suspension was filtered through diatomaceous earth, and the filter was washed with DCM. The mother liquor was evaporated to dryness, suspended in a small amount of DCM, stirred, filtered, and washed with pentane. After filtration and drying, 1.12 g (73%) of yellow powder was obtained.

[0110] 1 H NMR (400MHz, CD2Cl 2, 298K) δ = 14.25 ppm.

[0111] X1041 Synthesis

[0112] A solution of sodium hexafluorophosphate in acetonitrile was added in portions to a solution of Mo(2,6-Me2PhN)(CHCMe2Ph)(IMes)(2,6-Cl2PhO)(OTf) (500 mg) in 6 mL of DCM at 25 °C. The reaction mixture was stirred at 25 °C for 3 hours. The orange-yellow suspension was evaporated to dryness. The solid was separated by decantation in toluene, and the toluene was evaporated three times. The residue was dissolved in DCM and filtered through diatomaceous earth, with the filter pad washed with DCM. The mother liquor was evaporated to dryness, and the resulting yellow solid was ground in pentane. After filtration and drying, 327 mg (63%) of yellow powder was obtained.

[0113] 1 H NMR (400MHz, CD2Cl 2, 298K) δ = 14.05 (s, alkylene, 1H), 7.26-7.21 (m, ArH, 3H), 7.24 (s, tricresyl ArH, 4H), 7.13 (m, ArH, 2H), 7.06 (m, ArH, 1H), 6.99 (m, ArH, 2H), 6.73 (t, ArH, 1H), 6.72 (s, IMes =CH, 2H), 6.70 (d, ArH, 2H), 2.36 (s, imino Me, 6H), 2.19 (s, tricresyl Me, 6H), 2.01 (s, tricresyl Me, 6H), 2.00 (s, tricresyl Me, 6H), 1.84 (s, neobenzyl, 3H), 1.69 (wide s, neobenzyl Me, 3H), 1.56 (s, MeCN Me, 3H) 19 F NMR (376MHz, CD2Cl2, 298K) δ = -73.4 (d, 1JP-F= 708.6Hz, 6F).

[0114] Metathesis reaction of terminal alkenes Based on the test reactions using terminal olefins, molybdenum NHC bis(trifluoromethanesulfonate), tungsten NHC dibromide, and molybdenum NHC mono(trifluoromethanesulfonate)-monaryloxy complexes exhibited lower activity at a catalyst loading of 100 ppm compared to cationic molybdenum and tungsten NHC complexes.

[0115] Cationic molybdenum and tungsten NHC complexes exhibit significantly higher activity, with cationic molybdenum NHC aryloxy complexes showing extremely high catalytic activity even below 100 ppm. Furthermore, cationic molybdenum aryloxy derivatives exhibit high E-selectivity.

[0116] Cross-metathesis reaction of 1-decene and methyl 9-decenoate

[0117] Yield (%) = 100 x n(P) / n(9DAME). The maximum yield achievable in a closed system is 50% when the starting material ratio is 1:1.

[0118] Table 5 shows the results of the cross metathesis reaction of 1-decene and 9-decenoate methyl esters using cationic Mo- and W-NHC.

[0119] Table 5

[0120] Table 6 shows the cross metathesis reaction of 1-decene and methyl 9-decenoate using selected cations Mo- and W-NHC (X948 to X954) at a concentration of 75 ppm, and compares it with the MAP catalysts (X002 to X211) in Table 1.

[0121] Table 6

[0122] Autorecomposition reaction of 1-decene

[0123] Table 7 shows the results of the autoregression reaction of 1-decene using the compounds according to the invention and the comparative complexes in Table 1.

[0124] Table 7

[0125] Autorecombination reaction of methyl 9-decenoate

[0126] Table 8 shows the results of the autoregression reaction of methyl 9-decenoate using the compounds according to the invention and the comparative complexes in Table 1.

[0127] Table 8

[0128] Scale-up experiment of autorecombinant decomposition reaction of methyl 9-decenoate. In a 2 L round-bottom flask, 265 mg X948 (75 ppm) was added to 389 g of methyl 9-decenoate. The reaction mixture was stirred at 25 °C for 3 h under a dynamic vacuum of 50 mbar. 1 mL of methanol was added to the reaction mixture, and the product was separated by vacuum distillation. 300 g of (E)-9-octadecenoate dimethyl ester was obtained (yield 42%, based on a theoretical maximum of 50%). The E / Z ratio determined by GC was 97 / 3.

[0129] Cross metathesis reaction of (Z)-1,3-hexadiene with methyl 9-decenoate

[0130] Using the Z-selective catalyst X211, the conjugated diene (Z)-1,3-hexadiene and methyl 9-decenoate undergo a cross metathesis reaction to obtain methyl (Z,Z)-9,11-tetradecadienoate; using the E-selective catalysts X948 and X971, another stereoisomer (E,Z)-9,11-tetradecadienoate is obtained.

[0131] Table 9 shows the results of the cross metathesis reaction of (Z)-1,3-hexadiene with methyl 9-decenoate using the complexes according to the present invention and the comparative complexes in Table 1.

[0132] Table 9

[0133] Cross-metathesis reaction of allyl acetate (AAc) and methyl 9-decenoate

[0134] When n(AAc) / n(9DAME) = 2, the maximum yield is 66%.

[0135] Table 10 shows the results of the cross metathesis reaction of allyl acetate (AAc) with methyl 9-decenoate using the complexes according to the present invention and the comparative complexes in Table 1.

[0136] Although the cross metathesis reaction between allyl acetate and methyl 9-decenoate did not occur in the presence of a MAP-type catalyst, the cationic molybdenum NHC aryloxy complex X948 proved to be an excellent catalyst for this conversion reaction.

[0137] Table 10

[0138] Cross-metathesis reaction of allyl acetate and methyl 9-decenoate, synthesis of methyl (E)-11-acetoxy-undecenoate, scale-up experiment 375 g of allyl acetate and 345 g of methyl 9-decenoate were mixed in a 2 L round-bottom flask equipped with a reflux condenser. 0.85 mL of methylaluminoxane (MMAO) (7 wt% in toluene, 350 ppm) was added, and the mixture was stirred at 25 °C for 4 h. After the pretreatment period, 460 mg of X948 (50 ppm) was added, and the reaction mixture was stirred at 25 °C under dynamic vacuum (500 mbar) for 4 h, followed by stirring at atmospheric pressure for another 20 h. 1 mL of methanol was added to the reaction mixture, and the product was separated by vacuum distillation. 281 g of (E)-11-acetoxy-undecenoate methyl ester (yield = 58%) was given. The E / Z ratio was determined to be 97.8 / 2.2 by gas chromatography.

[0139] 1 H NMR (300MHz, CDCl 3, 296K) δ = 5.76 (ttd, 3 J CH->CH = 15.3Hz, 3 J CH-CH2 = 6.7Hz, 4 J CH->CH2 =1.0Hz, -O-CH2-CH=CH-, 1H), 5.55 (ttd, 3 J CH->CH = 15.3Hz, 3 J CH-CH2 = 6.4Hz, 4 J CH->CH2-O =1.3Hz, -O-CH2-CH=CH-, 1H), 4.50 (qd, 3 J O-CH2->CH = 6.4Hz, 4 J O-CH2->CH = 1.3Hz, 5 J O-CH2->CH2 <1Hz, -O-CH2-CH=CH-, 1H), 3.66 (s,Me-OC(O)-, 3H), 2.30 (t, 3 JCH2->CH2 =7.7Hz, Me-OC(O)-CH2-, 2H), 2.06 (s, Me-C(O)-O, 3H), 2.04 (wide q, =CH-CH2-CH2-,2H), 1.61 (wide quintet, Me-OC(O)-CH2-CH2-, 2H), 1.35-1.29 (m, -CH2-, 8H) ppm.

[0140] Metathesis reaction of internal alkenes Cross metathesis reaction of (E)-9-octadecene and methyl 9-decenoate

[0141] Table 11 shows the results of the cross-metathesis reaction between (E)-9-octadecene and methyl 9-decenoate. Molybdenum and tungsten metathesis catalysts generally exhibit low reactivity towards internal alkenes. However, the cationic Mo / W NHC complex showed higher activity than the MAP catalysts tested from Table 1. The cationic NHC complex also showed the ability to cleave the C=C double bond of trans-olefins.

[0142] Table 11

[0143] Cross metathesis reaction of (Z)-9-octadecene and methyl 9-decenoate

[0144] Table 12 shows the results of the cross metathesis reaction between (Z)-9-octadecene and methyl 9-decenoate.

[0145] Table 12

[0146] Ethylene hydrolysis of methyl transoleate ((E)-9-octadecenoate methyl ester)

[0147] Unlike other Mo / W complexes, the ethyleneolysis of the trans double bond can also be achieved using a cationic NHC catalyst.

[0148] Table 13 shows the results of the ethyleneolysis reaction of methyl transoleate ((E)-9-octadecenoate methyl ester) at an exemplary temperature of 50°C.

[0149] Table 13

Claims

1. Compounds of Formula I in: M is Mo or W; NHC is a nitrogen-containing heterocyclic carbene, which is bonded to M through its carbene carbon atom; X is =NR 1 ; Y represents an alkylene or arylene group = CR 2 R 3 ; Z represents an aryloxy residue -OR 4 ; L is a neutral ligand; n is 0 or 1; A is a noncoordinate anion; in: R 1 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; R 2 and R 3 Independently, each -C can be arbitrarily replaced. 1-10 Alkyl or -C 6-14 Aryl, or -H, where R 2 and R 3 Not both H; R 4 It is a phenyl group or a phenyl group substituted with at least one halogen atom; The prerequisite is that the compound of formula I is not a compound of any of the following formulas: 。 2. Compounds of Formula II in: M is either Mo or W; Mo is preferred. NHC is a nitrogen-containing heterocyclic carbene, which coordinates with M through its carbene carbon atom; X is =NR 1 ; Y represents an alkylene or arylene group = CR 2 R 3 ; Z represents an alkoxy or aryloxy residue -OR 4 ; L is a neutral ligand; n is 0 or 1; A is a noncoordinate anion; in: R 1 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; R 2 and R 3 Independently, each -C can be arbitrarily replaced. 1-10 Alkyl or -C 6-14 Aryl, or -H, where R 2 and R 3 Not both H; R 4 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; The prerequisite is that the compound of formula II is not a compound of any of the following formulas: ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ； Preferably, compounds of formula I as defined in claim 1 are also excluded.

3. The compound according to any one of claims 1 or 2, wherein, NHC is selected from the following NHC group: Nitrogen-containing heterocyclic carbene containing formula 6 Among them, R is defined in Equation 6 7 and R 8 Each can be independently H, unbranched or branched C. 1-20 Alkyl, C 5-9 Cycloalkyl or phenyl, wherein the phenyl group is optionally composed of up to three independently selected from unbranched or branched C4 groups. 1-6 Alkyl, C 1-6 Alkoxy or halogen groups are substituted, and In this configuration, the chemical bonds, indicated by wavy lines, are respectively connected to the optionally substituted alkenyl or alkylene groups, wherein the carbene carbon atom, the two nitrogen atoms, and the optionally substituted alkenyl or alkylene groups form a ring; or Nitrogen-containing heterocyclic carbene, including the part of formula 7 Wherein, Ar as defined in Formula 7 is an aryl group, preferably optionally substituted with one or more phenyl groups selected from the following: C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryl, C6-C 14 aryloxy or halogen; and The chemical bonds, indicated by wavy lines, are respectively connected to the optionally substituted alkenyl or alkylene groups, wherein the carbon atom, carbene carbon atom, nitrogen atom and the optionally substituted alkenyl or alkylene groups form a ring, which may optionally be bridged by the alkylene groups; Preferably, the carbene of formula 6 is a carbene of one of formulas 6a, 6b, 6c or 6d: , , or , Among them, R 9 and R 10 Each is independently H, unbranched or branched C. 1-20 Alkyl or phenyl, wherein the phenyl group is optionally composed of up to three C groups independently selected from unbranched or branched C groups. 1-6 Alkyl, C 1-6 Alkoxy or halogen group substitution; or R 9 and R 10 It combines with the carbon atoms it is attached to to form a 3- to 8-membered carbon ring, preferably an aromatic ring, more preferably C6H4; Y and Y' are halogens; More preferably, wherein NHC is formula 6a or formula 6b, and more preferably, R as defined in formula 6a or formula 6b 9 and R 10 H, and R as defined in equation 6a or 6b. 7 and R 8 It is trimethylbenzene or 2,6-diisopropylphenyl; or Wherein, NHC is the formula (n=1 to 8).

4. The compound according to any one of claims 1 to 3, wherein, NHC is selected from: 。 5. The compound according to claim 3, wherein, The carbene in Formula 7 is either Formula 7a or Formula 7b: In Equation 7a, each R is independently hydrogen, C1-C 12 Alkyl, C3-C 12 cycloalkyl, C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryloxy or halogen atom substitution; and wherein the two R atoms separated by the C-CR2-C portion can combine to form a ring system; or Carbene of type 7b In Equation 7b, each R is independently hydrogen, C1-C 12 Alkyl, C3-C 12 cycloalkyl, C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 The aryloxy or halogen atom is substituted; and, wherein n is 1, 2 or 3; preferably, wherein each R in formula 7b is independently hydrogen, C1-C 12 Alkyl or C3-C 12 cycloalkyl; Preferably, the ligand of formula 7a is formula 7a'. Among them, R in equation 7a' 12 R 13 R 14 and R 15 Each independently is hydrogen, C1-C 12 Alkyl, C3-C 12 cycloalkyl, C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryloxy or halogen atom substitution; and, wherein R 12 and / or R 13 Can be used with R 14 and / or R 15 Combining to form a ring system; or Among them, the ligand of formula 7b is formula 7b': Among them, R in equation 7b' 16 R 17 and R 18 Each is independently a hydrogen atom or a C1-C atom. 12 Alkyl, or C3-C 12 cycloalkyl, or C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryloxy or halogen atom substitution, preferably, wherein R in formula 7b' 16 R 17 and R 18 Each independently constitutes H, C1-C 12 Alkyl or C3-C 12 cycloalkyl; More preferably, NHC in Formula 7 is a carbene of Formula 7c. In Equation 7c, m is an integer from 0 to 4, and each R y Independently possessing C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryl, C6-C 14 The meaning of aryloxy or halogen; for example, carbene of formula 7c'. Or a 7d carbene In Equation 7d, m is an integer from 0 to 4, and each R y Independently possessing C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryl, C6-C 14 The meaning of aryloxy or halogen; for example, carbene of formula 7d'. Or a carbene of type 7e Or a carbene of formula 7f Or a carbene of formula 7g or 7h Or a carbene of type 7i Or a 7k carbene Furthermore, each R in formulas 7c to 7i is independently hydrogen or C1-C. 12 Alkyl, or C3-C 12 cycloalkyl, or C2-C 12 alkenyl, C6-C 14 Aryl, C1-C5 perfluoroalkyl, C7-C 24 Aryl or C6-C 14 Perfluoroaryl, optionally bonded by at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 14 Aryloxy or halogen atom substitution; preferably, each R in formulas 7c to 7i is hydrogen, C1-C 12 Alkyl or C3-C 12 Cycloalkyl.

6. The compound according to claim 1 and any one of claims 3 to 5, which are dependent on claim 1, wherein, For R 1 R 2 and R 3 For any of these, the term "optionally substituted" means that the substituent is independently selected from C. 1-5 Alkyl, C 1-5 Alkoxy, halogen, nitro, N(C) 1-5 Alkyl)2、-NH-C(O)C 1-5 Alkyl, phenyl, phenoxy, wherein the phenyl group in phenyl and phenoxy groups can be further converted into C 1-5 Alkyl, C 1-5 Alkoxy, halogen, nitro, N(C) 1-5 Alkyl)2、-NH-C(O)C 1-5 One or more alkyl groups are substituted; or According to claim 2 and the compound of any one of claims 3 to 5 which are dependent on claim 2, wherein, for R 1 R 2 R 3 and R 4 For any of these, the term "optionally substituted" means that the substituent is independently chosen from C. 1-5 Alkyl, C 1-5 Alkoxy, halogen, nitro, N(C) 1-5 Alkyl)2、-NH-C(O)C 1-5 The group consisting of alkyl, phenyl, and phenoxy groups, wherein the phenyl group in the phenyl and phenoxy groups can be further converted into C 1-5 Alkyl, C 1-5 Alkoxy, halogen, nitro, N(C) 1-5 Alkyl)2、-NH-C(O)C 1-5 One or more alkyl groups are substituted.

7. The compound according to any one of claims 1 to 6, wherein, R 2 and R 3 One of them is hydrogen, and R 2 and R 3 The other one is -C(CH3)3 or -C(CH3)2C6H5.

8. The compound according to claim 1 and any one of claims 3 to 7, which are dependent on claim 1, wherein, R 4 Selected from: phenyl; or A phenyl group containing only F as at least one halogen; or A phenyl group containing only Cl as at least one halogen; or A phenyl group containing only Br as at least one halogen; or A phenyl group containing F and Cl as at least one halogen; or A phenyl group containing F and Br as at least one halogen; or A phenyl group containing Cl and Br as at least one halogen; or A phenyl group containing F, Cl, and Br as at least one halogen.

9. The compound according to any one of claims 1 to 8, wherein, The neutral ligand L is selected from ethers, phosphine, nitrile or pyridine, dimethyl sulfoxide, acetone, dimethylformamide; preferably, the nitrile is selected from acetonitrile, tert-butyl nitrile and benzonitrile.

10. The compound according to any one of claims 1 to 9, wherein, The noncoordinated anion is selected from perchlorate [ClO4]. - Tetrafluoroborate [BF4] - hexafluorophosphate [PF6] - SbF6 (hexafluoroantimonate) - Tetraphenylborate [BPh4] - Tetra(trifluoromethyl)borate [B(CF3)4] - Tetra(pentafluorophenyl)borate [B(C6F5)4] - Tetra(3,5-bis(trifluoromethyl)phenyl)borate[B{(3,5-di-CF3)C6H3}4] - And tetra(nonafluorotert-butoxy)aluminate [Al{OC(CF3)3}4] - A group that is formed.

11. The compound according to claim 1, wherein, The compound is characterized by having the following formula: [M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L) n ]A Furthermore, the compounds mentioned are selected from compounds X945 to X968 and X979 to X954 in the table below, but exclude compound X973: ； or, The compound according to claim 2, wherein the compound is characterized by having the following formula: [M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L)]A Furthermore, the compound in question is X973.

12. Compounds of Formula III in: M is Mo or W; NHC is a nitrogen-containing heterocyclic carbene, which coordinates with M through its carbene carbon atom; X is =NR 1 ; Y represents an alkylene or arylene group = CR 2 R 3 ; Z represents trifluoromethanesulfonate (TfO); or a halide selected from Cl- or Br-; or -OR. 4 , where R 4 To arbitrarily replace C 1-10 Alkyl or C 6-14 Aryl; L is a neutral ligand or an anionic ligand, wherein the anionic ligand is trifluoromethanesulfonate; or is selected from Cl. - or Br - halides; n is 0 or 1; A is a noncoordinate anion; m is 0 or 1; in: R 1 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; R 2 and R 3 Independently, each -C can be arbitrarily replaced. 1-10 Alkyl or -C 6-14 Aryl, or -H, where R 2 and R 3 Not both H; In the compounds of formula III: (i) Z and L are TfO or Br respectively, and n is 1 and m is 0; or (ii) Z is OR 4 And L is TfO or Br, and n is 1 and m is 0; or (iii) Z is either TfO or Br, L is a neutral ligand, n is 0 or 1 and m is 1; Furthermore, the compound is characterized by having the following formula: [M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L)] And wherein the compound is selected from compounds X359 to X944 in the table below; or The compound is characterized by having the following formula: [M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L) n ]A Furthermore, the compound is selected from compounds X930 to X963 in the table below: 。 13. A method for carrying out a double displacement reaction, comprising: React the compound as defined in any one of claims 1 to 11 with one or more olefins; or React the compound of formula III with one or more olefins. in: M is Mo or W; NHC is a nitrogen-containing heterocyclic carbene, wherein the nitrogen-containing heterocyclic carbene is coordinated with M through its carbene carbon atom; wherein NHC is defined in any one of claims 3 to 5; X is =NR 1 ; Y represents an alkylene or arylene group = CR 2 R 3 ; Z represents trifluoromethanesulfonate (TfO); or a halide selected from Cl- or Br-; or -OR. 4 , where R 4 To arbitrarily replace C 1-10 Alkyl or C 6-14 Aryl; L is a neutral ligand or an anionic ligand, wherein the anionic ligand is trifluoromethanesulfonate; or is selected from Cl. - or Br - halides; n is 0 or 1; A is a noncoordinate anion; m is 0 or 1; in: R 1 To arbitrarily replace -C 1-10 Alkyl or -C 6-14 Aryl; R 2 and R 3 Independently, each -C can be arbitrarily replaced. 1-10 Alkyl or -C 6-14 Aryl, or -H, where R 2 and R 3 Not both H; In the compounds of formula III: (iii) Z is either TfO or Br, L is a neutral ligand, n is 0 or 1 and m is 1; Preferably, the compound of formula III is characterized by having the following formula: [M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L) n ]A Furthermore, the compound is selected from compounds X930 to X963 as defined in claim 12.

14. The method according to claim 13, wherein, The metathesis reaction is E - Selective.

15. A compound of one of the following formulas is used for E Applications of selective olefin metathesis reactions: ， ， ， ， ,or ; or, Use of the compound of claim 12 as a starting material or intermediate for the synthesis of the compound as defined in any one of claims 1 to 11.

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