Metathesis composition containing an air-stable imidoalkylidene complex

Abstract

The present invention relates to compositions comprising a shrock-alkylidene complex having a neutral ligand selected from 1,10-phenanthroline and 2,2'-bipyridine, and one or more compounds containing an olefin double bond. When the complex is non-dissociative, it can be thermally activated to initiate a metathesis reaction in the composition. The present invention further relates to compositions comprising a shrock-alkylidene complex having a neutral 2,2'-bipyridine ligand, and one or more compounds containing an olefin double bond, wherein the complex is self-activating.

Description

[Technical Field]

[0001] The present invention relates to a composition capable of undergoing a metathesis reaction, comprising an 18-electron molybdenum or tungsten alkylidene complex formed by a 14-electron molybdenum or tungsten alkylidene complex and a neutral bidentate ligand such as 1,10-phenanthroline or 2,2'-bipyridine, and one or more compounds, each containing an olefin double bond. The complexes contained in the composition can be activated by heat to initiate a metathesis reaction. The present invention further relates to a method for preparing the composition and a method for activating the composition. [Background technology]

[0002] Olefin metathesis reactions catalyzed by transition metal catalysts, such as molybdenum or tungsten alkylidene catalysts, also known as Schroch catalysts, are among the most important reactions in organic synthesis chemistry. Known beneficial types of catalysts include the Mo(VI) and W(VI) alkylidene complexes. Their effectiveness depends on the type of metal, alkylidene group, and ligand. While such catalysts have proven effective, they often lack stability in air, which makes them more difficult to handle and frequently limits their usefulness.

[0003] To improve air stability, International Publication No. 2012 / 116695 (Fuertner) proposes stabilizing such catalysts by complexing them with bidentate heterocycles such as 1,10-phenanthroline and 2,2'-bipryridine. Exemplary 1,10-phenanthroline complexes are, for example, complexes 5-8. [ka] In the formula, R 24 =methyl, phenyl, R 25 , R 26 =H, methyl, CF3, and Z = methyl, isopropyl, halogen.

[0004] However, although such air-stable products are not catalytically active, the catalytic active form was known to be released upon exposure to Lewis acids such as MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. The presence of Lewis acids and the formation of phenanthroline adducts with Lewis acids generally result in a complex workup of the reaction mixture for isolating the reaction products.

[0005] European Patent No. 3 268 377(B1) (XiMo AG) discloses a tungstenimide alkylidene catalyst stabilized with 1,10-phenanthroline. The catalyst must be activated by the addition of a Lewis acid such as zinc chloride. Activation is carried out in an inert solvent such as toluene. Exemplary complexes are complexes III to VI. [ka]

[0006] The scientific literature from J. Heppekausen and A. Furstner, "Rendering Schrock-type Molybdenum Alkylidene Complexes Air Stable: User-friendly Precatalysts for Alkene Metathesis," Angew. Chem. Int. Ed. 2011, 50, 7829-7832, https: / / doi.org / 10.1002 / anie.201102012, discloses Schrock-catalyzed phenanthroline and bipyridine complexes 2, 3, 5, and 7 that, as determined by NMR spectroscopy, do not show signs of partial dissociation (to 1, 4, or 6) in solvent at room temperature. [ka] Ar=2,6-diisopropylphenyl.

[0007] The authors state that complexes 2, 3, 5, and 7 lack catalytic activity even at higher temperatures.

[0008] British Patent No. 2537416 describes the following in Examples 3 and 6: [ka] Metathesis catalysts complexed with 2,2'-bipyridine and substituted bipyridines have been disclosed that can be activated by dissolving in an aprotic solvent such as deuterium-benzene without the need for the addition of a Lewis acid, as they spontaneously dissociate (see Examples 10 and 11 of British Patent No. 2 537 416). The inventors of British Patent No. 2 537 416 refer to the spontaneous liberation of the activated catalyst in the solvent as a "self-activating catalyst."

[0009] This reference does not use solvents, [ka] Further disclosures describe the homometathesis reaction of allylbenzene at room temperature catalyzed by [the compound]. This complex is self-activating at room temperature, i.e., it dissociates into a 14-electron system and bipyridine. The conversion rate after 16 hours was 54.2%.

[0010] The concept of self-activation of bipyridine adducts is also published in scientific literature (Gulyas, H. et al. "Air-stable 18-electron adducts of Schrock catalysts with tuned stability constants for spontaneous release of the active species", Commun. Chem. 4, 71 (2021); https: / / doi.org / 10.1038 / s42004-021-00503-4). This reference discusses compounds as catalysts. [ka] Homometathesis of methyl oleate in benzene at a temperature of 80°C using [a specific method] and ring-closing metathesis of diethyldiallyl malonate in benzene at room temperature are disclosed.

[0011] This reference includes compounds as catalysts. [ka] The ring-opening metathesis polymerization of norbornene in toluene at 25°C using the method described is further disclosed.

[0012] International Publication No. 2021 / 239891 (Verbio) discloses a schrock-alkylidene complex containing the phenanthrene ligand D defined therein in the following formula. [ka]

[0013] The inventors of International Publication No. 2021 / 239891 describe a 5L measurement at 298K. * mol -1 ~250,000L * mol -1 We discovered that the Schrock-alkylidene complex of the above formula, having a stability constant in the range of K, is air-stable and catalytically active in olefin metathesis reactions without the need to remove the bidentate ligand with a Lewis acid, and therefore without unnecessarily forming the corresponding byproduct; in other words, such a complex is self-activating. Thus, this finite stability constant K helps to balance, in a selected solvent, an 18-electron complex containing a bidentate ligand and not active in olefin metathesis reactions, with a 14-electron complex in which the bidentate ligand is released by dissociation and is catalytically active in olefin metathesis reactions.

[0014] This reference document describes that in Example 7, a compound was used as a catalyst. [ka] Ethenolysis of FAME (fatty acid methyl ester) in benzene at 50°C using [a specific method / tool] is disclosed.

[0015] The above complex is self-activating. Its finite stability constant depends on the properties of the solvent. For example, at room temperature (298 K) under similar conditions, the complex dissociates considerably more readily in CD2Cl2 than in C6D6. Dissociation is even more favorable in CDCl3. [Overview of the Initiative]

[0016] Problems that the invention aims to solve There is a continuous need in industry for a composition that can carry out olefin metathesis reactions, in which the complex used to initiate the reaction has improved air stability, and when the complex or adduct and the substrate to be metathesis are mixed at room temperature, it does not become chemically activated and simplifies handling in processing, without the risk of premature and uncontrollable reactions caused by the high activity of the 14-electron complex (parent complex) or the dissociation (self-activation) of the 18-electron adduct.

[0017] Summary of the Invention This objective is achieved with the composition described in claim 1, i.e., a composition capable of performing a metathesis reaction, and this composition is (X) To form an 18-electron alkylidene compound, (a) 1,10-phenanthroline (optionally substituted) and (b) 2,2'-bipyridine (optionally substituted) A 14-electron shrock alkylidene compound that forms a complex with a bidentate ligand selected from, (Y) Each comprises one or more compounds containing an olefin double bond, This composition, (c) Does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. (d) The temperature is above 50°C.

[0018] In a preferred embodiment, the composition is (e) Does not contain an inert solvent for compound (X) and / or compound (Y).

[0019] (e) The absence of an inert solvent for compound (X) and / or compound (Y) results in a metathesis product with a high melting point, which may be beneficial for compositions where the solvent to be removed would require additional processing.

[0020] The inventors have discovered that an 18-electron alkylidene compound (X) can be modified to remain non-dissociative at least up to room temperature in a composition comprising the 18-electron alkylidene compound (X) and one or more compounds (Y), each containing an olefin double bond to be metathesis. This allows for proper mixing without any premature reaction and provides sufficient process time, even when the composition does not contain an inert solvent for compound (X) and / or compound (Y). This is important when the reaction is carried out on an industrial scale, because such a reaction must be controllable.

[0021] The inventors of this invention further, 1By 1H NMR analysis, it has been discovered that, even when dissociation of a 14-electron Schrock alkylidene compound of an 18-electron alkylidene compound into a bidentate compound is not observed up to at least room temperature, the metathesis reaction can be initiated at a higher temperature without requiring chemical activation. The inventors of the present invention refer to this effect as thermal activation. This could not have been predicted considering the previous assumption that only compounds lacking a neutral bidentate ligand are active (see J. Heppekausen and A. Fürstner mentioned in the Background section).

[0022] As used herein, the term "non-dissociative complex" means that the complex is thermodynamically stable up to at least room temperature. Thermodynamically stable means that the complex (adduct) or substrate dissolved or dispersed in a solvent does not dissociate significantly enough to be observed by 1 1H NMR spectroscopy.

[0023] This is in stark contrast to the self-activating (dissociative) complexes described in the Background section, which apparently appear to be thermodynamically unstable because dissociation can be easily detected by 1 1H NMR spectroscopy.

[0024] In a preferred embodiment, compound (X) has a stability constant in a solvent at 298 K that exceeds a value of 250,000 L * mol -1 , the solvent is one or more compounds (Y) each containing an olefin double bond, and / or the solvent is an inert solvent for compound (X) and / or compound (Y), and the stability constant is determined as defined herein. The drawings show the following.

Brief Description of the Drawings

[0025] [Figure 1] The complex at room temperature known from Heppekausen and Fürstner mentioned in the Background section

Chemical Formula

[0026] Composition according to the present invention

[0027] The present invention relates to a composition capable of performing a metathesis reaction, and this composition, (X) Forms an 18-electron alkylidene complex, (a) 1,10-phenanthroline (optionally substituted) and (b) 2,2'-bipyridine (optionally substituted) A 14-electron shrock alkylidene compound that forms a complex with a bidentate ligand selected from, (Y) Each comprises one or more compounds containing an olefin double bond, This composition, (c) Does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. (d) The temperature is above 50°C.

[0028] In a preferred embodiment, the composition is (e) Does not contain an inert solvent for compound (X) and / or compound (Y).

[0029] In one embodiment, the present invention relates to a composition, and this composition is (X1) Compound of formula I [ka] (Y) Each comprises one or more compounds containing an olefin double bond, During the ceremony, M is either Mo or W. A is NR 1 Alternatively, selected from O, in the formula, R 1 These are C, which is replaced by each of the optional substitutions. 1~10 It is alkyl or aryl, B is selected from pyrrole, indole, and pyrazole, each substituted as optional, C is OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, or B is identical to C, and C is OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, or Unlike C, B and C are both OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, (a) D is 1,10-phenanthroline or substituted 1,10-phenanthroline, R 3 and R 4 H and C are independent of each other. 1~10 Alkyl or aryl, C 1~10Alkyl and aryl groups are optionally substituted, R 3 and R 4 Only one of them is hydrogen. This composition, (c) Does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. (d) The temperature is above 50°C.

[0030] In a preferred embodiment, the composition is (e) Does not contain an inert solvent for compound (X) and / or compound (Y).

[0031] In a further embodiment, the present invention relates to a composition, (X2) Compound of formula II [ka] (Y) Each comprises one or more compounds containing an olefin double bond, During the ceremony, M is either Mo or W. A is NR 1 Alternatively, selected from O, in the formula, R 1 These are C, which is replaced by each of the optional substitutions. 1~10 It is alkyl or aryl, B is selected from pyrrole, indole, and pyrazole, each substituted as optional, C is OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, or B is identical to C, and C is OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, or Unlike C, B and C are both OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, (b) D is 2,2'-bipyridine or substituted 2,2'-bipyridine, R 3 and R 4 H and C are independent of each other. 1~10 Alkyl or aryl, C 1~10 Alkyl and aryl groups are optionally substituted, R 3 and R 4 Only one of them is hydrogen. This composition, (c) Does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. (d) The temperature is above 50°C.

[0032] In a preferred embodiment, the composition is (e) Does not contain an inert solvent for compound (X) and / or compound (Y).

[0033] According to the present invention, M is Mo or W.

[0034] In one embodiment, M is W.

[0035] In another embodiment, M is Mo.

[0036] According to the present invention, A is NR 1 Or selected from O, in the formula, R 1These are optionally substituted alkyl groups, preferably C 1~10 It is alkyl or aryl.

[0037] In a preferred embodiment, A is NR 1 And in the formula, R 1 These are C, which is replaced by each of the optional substitutions. 1~10 It is alkyl or aryl.

[0038] As used herein, for example, R 1 The definition used for "alkyl or C" 1~10 The term "alkyl" includes linear alkyl, branched alkyl, cyclic alkyl, and alicyclic alkyl. Preferred C 1~10 Alkyl is C 1~5 It is alkyl. In another embodiment, C 4~10 Alkyl is preferred.

[0039] In one embodiment, R 1 Alkyl groups such as t-butyl or 1-adamantyl are used.

[0040] As used herein, for example, R 1 The term "aryl" as used in the definition includes phenyl, naphthyl, anthracenyl, and phenanthryl as optionally substituted, respectively.

[0041] Preferred substituents are C 1~10 Alkyl, C 1~10 One or more of the following can be selected: alkoxy, phenyl, halogen, CN, and CF3.

[0042] Phenyl is preferred as the aryl group.

[0043] In one embodiment, R 1 C 1~10 Alkyl, C 1~10 C is independently substituted with one or more of the following: alkoxy, phenyl, halogen, CN, and CF3. 1~10 It is alkyl or phenyl.

[0044] According to the present invention, in one embodiment, B is selected from pyrrole, indole, and pyrazole, each optionally substituted.

[0045] In one embodiment, B is C 1~5 Alkyl, C 1~5 The compounds are selected from pyrrole, indole, and pyrazole, each independently substituted with one or more alkoxys or phenyls.

[0046] According to the present invention, C is OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is either alkyl)3Si or (aryl)3Si.

[0047] In a preferred embodiment, R 2 It is an electron-withdrawing group. The term "electron-withdrawing group" has a widely accepted meaning in this art.

[0048] In one embodiment, R 2 This is a phenyl compound substituted with -(CH2)4- to form a fused ring with phenyl, or with -(CH=CH-CH=CH)- to form a fused ring with phenyl. In this specification, the fused ring may be substituted with O-silyl.

[0049] The term "silyl" can refer to any silyl group that forms a covalent bond between silicon and oxygen. Preferred silyl groups include, for example, t-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and triphenylsilyl.

[0050] Similarly, (C 1~10 The terms alkyl)3Si or (aryl)3Si encompass the silyl group as defined above.

[0051] According to the present invention, D is a neutral bidentate ligand.

[0052] In compound (X1) of formula I, the neutral ligand is (a) 1,10-phenanthroline or substituted 1,10-phenanthroline. Both N atoms of the phenanthroline skeleton are bonded to M, thus forming a bidentate ligand, and therefore an 18-electron alkylidene compound.

[0053] In one embodiment, phenanthroline is substituted. In a preferred embodiment, phenanthroline is substituted with one or more electron-donating groups. The term "electron-donating group" has a meaning widely accepted in the art.

[0054] In one embodiment, 1,10-phenanthroline is independently C 1~5 Alkyl, C 1~5 Alkoxy, -O-(CH2) n The group is substituted with one or more of the following: -O-(n=1 or 2) and phenyl. These groups represent electron-donating groups in the sense of the present invention.

[0055] Commercially available substituted 1,10-phenanthrolines containing electron-donating substituents are 4,7-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 4,7-dimethoxy-1,10-phenanthroline, 3,8-dimethyl-1,10-phenanthroline, 3,8-dimethoxy-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethoxy-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 5,6-diphenyl-1,10-phenanthroline, 5,6-dimethoxy-1,10-phenanthroline, and 1,10-phenanthroline[5,6-d]-1,3-dioxole.

[0056] In a more preferred embodiment, C is an electron-withdrawing group and 1,10-phenanthroline is unsubstituted.

[0057] In a more preferred embodiment, C is an electron-withdrawing group and 1,10-phenanthroline is substituted with one or more of the electron-donating groups defined above.

[0058] In a more preferred embodiment, B is the same as C, C is an electron-withdrawing group, and 1,10-phenanthroline is unsubstituted.

[0059] In a more preferred embodiment, B is the same as C, C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more of the electron-donating groups defined above.

[0060] In a more preferred embodiment, B is different from C, but both B and C are electron-withdrawing groups, and D is 1,10-phenanthroline or 1,10-phenanthroline substituted with one or more of the electron-donating groups defined above.

[0061] In one embodiment, B is selected from pyrrole, indole, and pyrazole, each optionally substituted, C is selected from O-R 2 selected from, R 2 is C substituted with one or more of halogen or CF3 each 1~10 alkyl or aryl or (C 1~10 alkyl)3Si or (aryl)3Si, or (C 1~10 alkyl)3Si or (aryl)3Si is selected from t-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and triphenylsilyl, and 1,10-phenanthroline is unsubstituted or C 1~5 alkyl, C 1~5Alkoxy, -O-(CH2) n -O-(n = 1 or 2), and is substituted with one or more selected from phenyl.

[0062] In one embodiment, B is optionally selected from pyrrole, indole, and pyrazole each substituted, C is (CF3)3CO-, (CCl3)(CF3)2CO-, (C6H5)(CF3)2CO-, (CH3)(CF3)2CO-, ClC6H4O-, Cl2C6H3O-, Cl3C6H2O-, BrC6H4O-, Br2C6H3O-, Br3C6H2O-, CF3C6H4O-, (CF3)2C6H3O-, Cl(CF3)C6H3O-, tert-butyldimethylsilyloxy (TBSO, TBDMSO), trimethylsilyloxy (trimethylsilyloxy, TMSO), triethylsilyloxy (triethylsilyloxy, TESO), triisopropylsilyloxy (TIPS)O, tert-butyldiphenylsilyloxy (t-butyldiphenylsilyloxy, TBDPSO), and triphenylsilyloxy, and 1,10-phenanthroline is unsubstituted or 4,7-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 4,7-dimethoxy-1,10-phenanthroline, 3,8-dimethyl-1,10-phenanthroline, 3,8-dimethoxy-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethoxy-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 5,6-diphenyl-1,10-phenanthroline, 5,6-dimethoxy-1,10-phenanthroline, and 1,10-phenanthroline[5,6-d]-1,3-dioxole.

[0063] In one embodiment, B is the same as C, and C is selected from O-R 2 wherein, R 2 is C substituted with one or more of halogen or CF3 respectively 1~10 alkyl or aryl or (C 1~10It is either alkyl)3Si or (aryl)3Si, or (C 1~10 Alkyl)3Si or (aryl)3Si is t-butyldimethylsilyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldiphenylsilyl, or triphenylsilyl, and 1,10-phenanthroline is unsubstituted or C 1~5 Alkyl, C 1~5 Alkoxy, -O-(CH2) n It is substituted with one or more molecules selected from -O-(n=1 or 2) and phenyl.

[0064] In another embodiment, B is the same as C, and C is selected from (CF3)3CO-, (CCl3)(CF3)2CO-, (C6H5)(CF3)2CO-, (CH3)(CF3)2CO-, FC6H4O-, F2C6H3O-, F3C6H2O-, C6F5O-, ClC6H4O-, Cl2C6H3O-, Cl3C6H2O-, BrC6H4O-, Br2C6H3O-, Br3C6H2O-, CF3C6H4O-, (CF3)2C6H3O-, Cl(CF3)C6H3O-, t-butyldimethylsilyloxy, trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, t-butyldiphenylsilyloxy, and triphenylsilyloxy. ,10-phenanthroline is either unsubstituted or selected from 4,7-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 4,7-dimethoxy-1,10-phenanthroline, 3,8-dimethyl-1,10-phenanthroline, 3,8-dimethoxy-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethoxy-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 5,6-diphenyl-1,10-phenanthroline, 5,6-dimethoxy-1,10-phenanthroline, and 1,10-phenanthroline[5,6-d]-1,3-dioxole.

[0065] In another embodiment, B is different from C, and both B and C are OR 2Selected from, in the formula, R 2 Each is substituted with one or more of halogens or CF3, C 1~10 Alkyl or aryl or (C 1~10 It is either alkyl)3Si or (aryl)3Si, or (C 1~10 Alkyl)3Si or (aryl)3Si is t-butyldimethylsilyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldiphenylsilyl, or triphenylsilyl, and 1,10-phenanthroline is unsubstituted or C 1~5 Alkyl, C 1~5 Alkoxy, -O-(CH2) n It is substituted with one or more molecules selected from -O-(n=1 or 2) and phenyl.

[0066] In another embodiment, B differs from C, and both B and C are selected from (CF3)3CO-, (CCl3)(CF3)2CO-, (C6H5)(CF3)2CO-, (CH3)(CF3)2CO-, FC6H4O-, F2C6H3O-, F3C6H2O-, C6F5O-, ClC6H4O-, Cl2C6H3O-, Cl3C6H2O-, BrC6H4O-, Br2C6H3O-, Br3C6H2O-, CF3C6H4O-, (CF3)2C6H3O-, Cl(CF3)C6H3O-, t-butyldimethylsilyloxy, trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, t-butyldiphenylsilyloxy, and triphenylsilyloxy. 1,10-phenanthroline is either unsubstituted or selected from 4,7-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 4,7-dimethoxy-1,10-phenanthroline, 3,8-dimethyl-1,10-phenanthroline, 3,8-dimethoxy-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethoxy-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 5,6-diphenyl-1,10-phenanthroline, 5,6-dimethoxy-1,10-phenanthroline, and 1,10-phenanthroline[5,6-d]-1,3-dioxole.

[0067] The inventors of the present invention have discovered that such complexes of formula I are non-dissociative in the compositions according to the present invention, at least up to room temperature.

[0068] In compound (X1) of formula II, the neutral ligand is (b) 2,2'-bipyridine or substituted 2,2'-bipyridine. Both N atoms of the bipyridine skeleton are bonded to M, thus forming a bidentate ligand and thus an 18-electron alkylidene compound.

[0069] In a preferred embodiment, 2,2'-bipyridine is independently C 1~5 Alkyl, C 1~5It is substituted with one or more alkoxy and / or phenyl groups. These groups represent electron-donating groups in the sense of the present invention.

[0070] Examples of commercially available bipyridines having electron-donating groups include 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, and 5,5'-dimethoxy-2,2'-bipyridine.

[0071] In a more preferred embodiment, B is the same as C, C is an electron-withdrawing group, and 2,2'-bipyridine is either unsubstituted or substituted with one or more electron-donating groups as defined above.

[0072] In a more preferred embodiment, B is different from C, but both B and C are electron-withdrawing groups, and D is either 2,2'-bipyridine or 2,2'-bipyridine substituted with one or more electron-donating groups as defined above.

[0073] In a preferred embodiment, B is the same as C, and C is OR 2 Selected from, in the formula, R 2 These are C, which are substituted with halogen or CF3, respectively. 1~10 Alkyl or aryl or (C 1~10 It is either alkyl)3Si or (aryl)3Si, or (C 1~10 Alkyl)3Si or (aryl)3Si is selected from t-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and triphenylsilyl, and 2,2'-bipyridine is unsubstituted or C 1~5 Alkyl, C 1~5 It is a 2,2'-bipyridine substituted with one or more molecules selected from alkoxy and phenyl.

[0074] In a preferred embodiment, B is the same as C, and C is (CF3)3CO-, (CCl3)(CF3)2CO-, (C6H5)(CF3)2CO-, (CH3)(CF3)2CO-, FC6H4O-, F2C6H3O-, F3C6H2O-, C6F5O-, ClC6H4O-, Cl2C6H3O-, Cl3C6H2O-, BrC6H4O-, Br2C6H3O-, Br3C6H2O-, CF3C6H4O-, (CF3)2C6H3O-, Cl(CF3)C6 H3O-, or selected from t-butyldimethylsilyloxy, trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, t-butyldiphenylsilyloxy, and triphenylsilyloxy, and D is selected from 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, and 5,5'-dimethoxy-2,2'-bipyridine.

[0075] Furthermore, in this embodiment, B is different from C, and both B and C are OR 2 Selected from, in the formula, R 2 Each is substituted with one or more of halogens or CF3, C 1~10 Alkyl or aryl or (C 1~10 It is either alkyl)3Si or (aryl)3Si, or (C 1~10 Alkyl)3Si or (aryl)3Si is selected from t-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and triphenylsilyl, and D is 2,2'-bipyridine, or C 1~5 Alkyl, C 1~5 It is a 2,2'-bipyridine substituted with one or more molecules selected from alkoxy and phenyl.

[0076] In a more preferred embodiment, B differs from C, and both B and C are (CF3)3CO-, (CCl3)(CF3)2CO-, (C6H5)(CF3)2CO-, (CH3)(CF3)2CO-, FC6H4O-, F2C6H3O-, F3C6H2O-, C6F5O-, ClC6H4O-, Cl2C6H3O-, Cl3C6H2O-, BrC6H4O-, Br2C6H3O-, Br3C6H2O-, CF3C6H4O-, (CF3)2C6H3O-, Cl(CF3 )C6H3O-, or selected from t-butyldimethylsilyloxy, trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, t-butyldiphenylsilyloxy, and triphenylsilyloxy, and D is selected from 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, and 5,5'-dimethoxy-2,2'-bipyridine.

[0077] The inventors of the present invention have found that such complexes of formula II are typically non-dissociative in compositions according to the present invention at room temperature, or at least up to room temperature.

[0078] Therefore, in a preferred embodiment, the composition according to the present invention requires that the compound of formula I (X1) and the compound of formula II (X2) contained in the composition remain non-dissociative in the composition at least up to room temperature.

[0079] In one embodiment, the compound of formula I (X1) or the compound of formula II (X2) has a stability constant of 250,000 L when measured at 298 K. * mol -1 If the value exceeds this, the composition is referred to as non-dissociative. A more preferred range is 300,000 L when measured at 298 K. * mol -1 Over, or 350,000L * mol -1 Over, or 400,000L * mol -1It is extremely stable. This stability constant can be determined according to a known method using the law of mass action. See International Publication 2021 / 239891, mentioned in the background section.

[0080] Complexes with a stability constant K in a given solvent, such as compound (X2), which is practically infinite, i.e., complexes with an excessively high stability constant, are too stable to release the active form from the complex. This applies to complexes that require the assistance of a Lewis acid to remove a bidentate ligand, as is known from the prior art mentioned in the background section.

[0081] In another embodiment, the non-dissociative nature of compound I (X1) or compound II (X2) is evident from the reference prior art (J. Heppekausen and A. Furstner) mentioned in the background art section, 1 This can be verified by 1H NMR spectroscopy.

[0082] Figures 1 to 3 1 The 1H NMR spectrum is from the phenanthroline complex known from Heppekausen and Furstner, as mentioned in the background information section. [ka] This shows that when heated, the complex remains non-dissociated up to a temperature of at least 95°C. After cooling, the spectrum in Figure 4 is identical to the spectrum in Figure 1. The shift in the aliphatic region (isopropyl, methyl) is due to the temperature effect.

[0083] Possible dissociation can be detected by the different alkylidene proton chemical shifts in the 18-electron and 14-electron complexes. Possible (partial) dissociation is 1 It can also be quantitatively recorded by 1H NMR spectroscopy. Both methods are well known in the art.

[0084] According to the present invention, when the temperature exceeds 50°C, it is not necessary to add a Lewis acid such as zinc chloride to the complex of formula I or formula II to remove the bidentate ligand from the complex in order to form an activated 14-electron complex from the 18-electron complex. Rather, the complex of formula I or formula II is thermally activated, i.e., no chemical activation is required. Surprisingly, even at temperatures higher than 50°C where dissociation cannot be observed by NMR analysis, the thermally activated catalyst of formula I or formula II initiates the metathesis reaction. This was unpredictable considering the previous assumption that only compounds lacking a neutral bidentate ligand are active (see J. Heppekausen and A. Furstner mentioned in the background art section).

[0085] International Publication No. 2021 / 239891 provides guidance on the appropriate synthesis of individual non-dissociative complexes. This document discloses how the stability constant of a complex can be influenced by the appropriate selection of ligands in the complex. The inventors have found that when a complex is dissolved in a solvent to release an active form, i.e., a 14-electron complex, from an 18-electron complex, particularly by at least D(1,10-phenanthroline and substituted 1,10-phenanthroline), or by further ligands B and C, e.g., alkoxides, aryloxides, or substitution patterns relating to D and C, the stability constant K relating to a neutral bidentate ligand in the solvent is measured at 298 K in 5 L. * mol -1 ~250,000L * mol -1 We discovered that it can be adjusted to a certain range.

[0086] International Publication No. 2021 / 239891 discloses that in one embodiment, 1,10-phenanthroline is substituted with one or more electron-donating groups to increase the stability constant compared to a complex having the same substitution pattern with respect to A, B, and C, but with the bidentate ligand being unsubstituted 1,10-phenanthroline. In another embodiment, 1,10-phenanthroline is substituted with one or more electron-withdrawing groups to decrease the stability constant compared to a complex having the same substitution pattern with respect to A, B, and C, but with the bidentate ligand being unsubstituted 1,10-phenanthroline.

[0087] In another embodiment, the steric bulk, i.e., spatial expansion, of residue C is increased to reduce the stability constant compared to a complex having the same substitution pattern with respect to A, B, and D.

[0088] Therefore, the method defined in International Publication No. 2021 / 239891 can also be used for the individualized preparation of non-dissociative complexes of the compounds defined in the present invention under formulas I and II.

[0089] The contents of International Publication No. 2021 / 239891 are incorporated herein by reference in their entirety.

[0090] As used herein, the term "room temperature" is defined as a temperature of up to 25°C, preferably between 15 and 25°C. The term "room temperature" is used synonymously with the term "ambient temperature."

[0091] As used herein with respect to the compound of formula I (X1) and the compound of formula II (X2), the term "at least to room temperature" includes temperatures above 25°C. Therefore, this term may be used synonymously with the term "at least to room temperature and above."

[0092] In one embodiment, the compound of formula I (X1) or the compound of formula II (X2) remains non-dissociative up to a temperature of at least 50°C, 60°C, 70°C, 80°C, 100°C, or 120°C or higher.

[0093] In one embodiment, R 3 and R 4 H and C are independent of each other. 1~10 Alkyl or aryl, C 1~10 Alkyl or aryl is independently C 1~5 C substituted with one or more alkyl or halogen atoms 1~5 Alkyl, C 1~5 It is substituted with one or more of the following: alkoxy, phenyl, or halogen.

[0094] In one embodiment, the temperature of the composition according to the present invention is above 55°C, or above 60°C, or above 70°C, or above 80°C, or above 90°C, or above 100°C, or The temperature range is over 50°C to 140°C, over 55°C to 130°C, or over 60°C to 120°C.

[0095] According to the present invention, the composition does not contain Lewis acid.

[0096] In one embodiment, in a composition having a temperature of 50°C or lower, the molar ratio of a compound (Y) containing one or more compounds including an olefin double bond to a compound of formula I (X1) or a compound of formula II (X2) is greater than 2000, 4000, 6000, 8000, 10,000, 20,000, 30,000, or 40,000 compared to a composition having a temperature above 50°C.

[0097] In preferred embodiments, the composition does not contain an inert solvent for compound (X) and / or compound (Y). However, as used herein, this term does not preclude the use of a small amount of inert solvent for handling compound (X1) or compound (X2). Thus, as used herein, the term “the composition does not contain an inert solvent for compound (X) and / or compound (Y)” means that an inert solvent such as benzene or toluene or chlorobenzene or hydrocarbons may be present in the composition, and the molar ratio of one or more compounds, each containing an olefin double bond, to the inert solvent is greater than 200, or greater than 500, or greater than 1000, or greater than 2000.

[0098] Therefore, in a preferred embodiment, compound (Y) is a solvent, where the solvent does not contain any further solvents, such as benzene or toluene or chlorobenzene or an inert solvent such as a hydrocarbon.

[0099] In one embodiment, the compound of formula I is one of the following compounds 5-8 [ka] (In the formula, R 24 =methyl, phenyl, R 25 , R 26 (=H is methyl, CF3 and Z is methyl, isopropyl, halogen) selected from one of these. Or the following compounds III-VI [ka] Select from one of the following: or the following compounds [ka] (R=Me, Ph, and Ar=2,6-diisopropylphenyl) [ka] Select from one of the following: Alternatively, the compound of formula II is [ka] and [ka] Selected from.

[0100] Method for preparing a composition according to the present invention

[0101] The present invention further relates to a method for preparing a composition according to the present invention, wherein this method is To provide a compound (X) (or a compound of formula I (X1) or a compound of formula II (X2)) and one or more compounds (Y), The mixture of the provided compounds is heated to a temperature above 50°C, During the ceremony, The composition does not contain one or more of the following: MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

[0102] Methods of thermal activation

[0103] The present invention further relates to a method for activating compound (X) (or (X1) of formula I or (X2) of formula II as defined above) to initiate an olefin metathesis reaction in a composition comprising one or more compounds (Y), wherein the method is The method involves heating a composition containing compound (X) (or (X1) and (X2)) and compound (Y) to a temperature above 50°C. The composition does not contain one or more of the following: MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

[0104] The present invention further relates to a method for carrying out a metathesis reaction, and this method is The method involves heating a composition containing compound (X) (or (X1) of formula I or (X2) of formula II) and one or more compounds (Y) to a temperature above 50°C. The composition does not contain one or more of the following: MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

[0105] Further themes

[0106] The present invention further relates to a composition, The compound (X) defined above (or the compound of formula I (X1) or the compound of formula II (X2)), Each contains one or more compounds (Y) that include an olefin double bond, This composition does not contain one or more of the following: MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. This composition has a temperature of less than 50°C. Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

[0107] The present invention further relates to the use of the composition in a metathesis reaction, the use is, This includes heating the composition to a temperature above 50°C.

[0108] The present invention further relates to the use of a compound (X) (or a compound of formula I (X1) or a compound of formula II (X2) as defined above) for initiating a metathesis reaction in one or more compounds (Y), each containing an olefin double bond, wherein the use is The method involves heating a composition containing compound (X) (or (X1) and (X2)) and compound (Y) to a temperature above 50°C. The composition does not contain one or more of the following: MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

[0109] The compositions according to the present invention can be used in all kinds of olefin metathesis reactions.

[0110] In one embodiment, in the composition according to the present invention, one or more compounds, each containing an olefin double bond, are selected to undergo a cross-metathesis reaction (CM) including self-metathesis [(homo)-cross metathesis ((HCM)].

[0111] In another embodiment, in the composition according to the present invention, one or more compounds, each containing an olefin double bond, are selected to undergo a ring-closing metathesis reaction (RCM).

[0112] In another embodiment, in the composition according to the present invention, one or more compounds, each containing an olefin double bond, are selected to undergo a ring-opening metathesis reaction (ROM).

[0113] In another embodiment, in the composition according to the present invention, one or more compounds, each containing an olefin double bond, are selected to undergo ring-opening metathesis polymerization (ROMP).

[0114] In another embodiment, in the composition according to the present invention, one or more compounds, each containing an olefin double bond, are selected to undergo an acyclic diene metathesis reaction (ADMET).

[0115] The present invention further relates to the following items. 1. A composition capable of performing a metathesis reaction, wherein this composition is (X) To form an 18-electron alkylidene compound, (a) 1,10-phenanthroline (optionally substituted) and (b) 2,2'-bipyridine (optionally substituted) A 14-electron shrock alkylidene compound that forms a complex with a bidentate ligand selected from, (Y) Each comprises one or more compounds containing an olefin double bond, This composition, (c) Does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. (d) The temperature is above 50°C, (e) A composition containing an inert solvent for compound (X) and / or compound (Y). 2. (X1) Compound of formula I [ka] (In the formula, M is either Mo or W. A is NR 1Alternatively, selected from O, in the formula, R 1 These are C, which is replaced by each of the optional substitutions. 1~10 It is alkyl or aryl, B is selected from pyrrole, indole, and pyrazole, each substituted as optional, C is OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, or B is identical to C, and C is OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, or Unlike C, B and C are both OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, D is 1,10-phenanthroline or substituted 1,10-phenanthroline. R 3 and R 4 H and C are independent of each other. 1~10 Alkyl or aryl, C 1~10 Alkyl and aryl groups are optionally substituted, R 3 and R 4 (Containing only one of which is hydrogen) or (X2) Compound of formula II [ka] (In the formula, M is either Mo or W. A is NR 1 Alternatively, selected from O, in the formula, R 1These are C, which is replaced by each of the optional substitutions. 1~10 It is alkyl or aryl, B is selected from pyrrole, indole, and pyrazole, each substituted as optional, C is OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, or B is identical to C, and C is OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, or Unlike C, B and C are both OR 2 Selected from, in the formula, R 2 These are C, which are replaced by each of the optional choices. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, D is 2,2'-bipyridine or substituted 2,2'-bipyridine. R 3 and R 4 H and C are independent of each other. 1~10 Alkyl or aryl, C 1~10 Alkyl and aryl groups are optionally substituted, R 3 and R 4 The composition described in item 1, comprising (where only one of them is hydrogen). 3.R 1 However, C 1~10 Alkyl, C 1~10 C is independently substituted with one or more of the following: alkoxy, phenyl, halogen, CN, and CF3. 1~10 The composition described in item 2, which is alkyl or phenyl. 4. B is C 1~10 Alkyl, C 1~10The composition according to item 2 or 3, selected from pyrrole, indole, and pyrazole, each independently substituted with one or more alkoxys or phenyls. 5.R 2 However, C was replaced by an arbitrary choice. 1~10 A composition according to any one of items 2 to 4, selected from alkyl or phenyl. 6. A composition according to any one of items 1 to 5, wherein compound (X), or compound (X1) and compound (X2), are non-dissociative in the composition at least up to room temperature. 7. C is an electron-withdrawing group, and 1,10-phenanthroline is unsubstituted, or C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more electron-donating groups, or B is identical to C, C is an electron-withdrawing group, and 1,10-phenanthroline is not substituted, or B is identical to C, C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more electron-donating groups, or Unlike C, B and C are both electron-withdrawing groups, and 1,10-phenanthroline is unsubstituted, or Unlike C, B and C are both electron-withdrawing groups, and 1,10-phenanthroline is substituted with one or more electron-donating groups. B is identical to C, C is an electron-withdrawing group, and 2,2'-bipyridine is not substituted, or B is identical to C, C is an electron-withdrawing group, and 2,2'-bipyridine is substituted with one or more electron-donating groups. Unlike C, B and C are both electron-withdrawing groups, and 2,2'-bipyridine is unsubstituted, or Unlike C, B and C are both electron-withdrawing groups, and 2,2'-bipyridine is substituted with one or more electron-donating groups. Preferably, B is selected from pyrrole, indole, and pyrazole, each substituted by optional choice, and C is OR 2Selected from, in the formula, R 2 However, each is substituted with one or more of halogens or CF3, C 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, or B is identical to C, and C is OR 2 Selected from, in the formula, R 2 However, each C is substituted with one or more of either halogen or CF3. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, and 1,10-phenanthroline is either unsubstituted or C 1~5 Alkyl, C 1~5 Alkoxy, -O-(CH2) n 1,10-phenanthroline substituted with one or more selected from -O-(n=1 or 2) and phenyl, or B is identical to C, and C is OR 2 Selected from, in the formula, R 2 However, each C is substituted with one or more of either halogen or CF3. 1~10 Alkyl or aryl or (C 1~10 It is alkyl)3Si or (aryl)3Si, and 2,2'-bipyridine is either unsubstituted or C 1~5 Alkyl, C 1~5 The composition according to any one of items 2 to 6, as far as we can see with reference to claim 2, which is substituted with one or more selected from alkoxy or phenyl. 8. The composition according to item 1 or 7, wherein compound (X) (or (X1) and (X2)) is non-dissociative up to a temperature of 50°C. 9.R 3 and R 4 However, independently, H, C 1~10 Alkyl or aryl, C 1~10 Alkyl or aryl, independently, C 1~5 C substituted with one or more alkyl or halogen atoms 1~5 Alkyl, C 1~5A composition according to any one of items 2 to 8, which is substituted with one or more alkoxys, phenyls, or halogens. A composition according to any one of items 1 to 9, wherein, in a composition having a temperature of 10.50°C or lower, the molar ratio of compound (Y), each containing one or more compounds including an olefin double bond, to compound (X), or compound (X1) of formula I, or compound (X2) of formula II is greater than 2,000, 4,000, 6,000, 8,000, 10,000, 20,000, 30,000, or 40,000, compared to a composition having a temperature of 50°C or higher. 11. The temperature is above 55°C, or above 60°C, or above 70°C, or above 80°C, or above 90°C, or above 100°C, A composition according to any one of items 1 to 10, wherein the temperature is in the range of over 50°C to 140°C, over 55°C to 130°C, or over 60°C to 120°C. 12. Compound (X) is one of the following compounds 5-8 [ka] (In the formula, R 24 =methyl, phenyl, R 25 , R 26 (=H is methyl, CF3 and Z is methyl, isopropyl, halogen) selected from one of these. Or the following compounds III-VI [ka] Select from one of the following: or the following compounds [ka] (R=Me, Ph, and Ar=2,6-diisopropylphenyl) [ka] Select from one of the following: Or, [ka] and [Chemical formula] The composition according to any one of items 1 to 11, selected from 13. A method for preparing the composition according to any one of items 1 to 12, comprising: providing compound (X) and compound (Y); heating the provided mixture of compounds to a temperature above 50 °C, the composition does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2; the composition contains an inert solvent for compound (X) and / or compound (Y). 14. A method for activating compound (X) according to any one of items 1 to 12 to initiate an olefin metathesis reaction in a composition containing one or more compounds (Y) each containing an olefin double bond, comprising: heating the composition containing compound (X) and compound (Y) to a temperature above 50 °C, the composition does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2; the composition contains an inert solvent for compound (X) and / or compound (Y). 15. A method for performing a metathesis reaction, comprising: heating a composition containing compound (X) according to any one of items 1 to 12 and one or more compounds (Y) to a temperature above 50 °C, The composition does not contain a Lewis acid selected from one or more of the following: MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. A method comprising a composition containing an inert solvent for compound (X) and / or compound (Y). 16. A composition, It includes a compound (X) listed in any one of items 1 to 12 and one or more compounds (Y), The composition does not contain a Lewis acid selected from one or more of the following: MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. The composition has a temperature of less than 50°C. The composition contains an inert solvent for compound (X) and / or compound (Y). 17. Use of the composition described in item 16 in a metathesis reaction, This includes heating the composition to a temperature above 50°C. The composition contains an inert solvent for compound (X) and / or compound (Y) for use. 18. Use of compound (X) to initiate a metathesis reaction in a composition containing one or more compounds (Y) described in any one of items 1 to 12, The method includes heating a composition containing compound (X) and compound (Y) to a temperature above 50°C. The composition does not contain a Lewis acid selected from one or more of the following: MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. The composition contains an inert solvent for compound (X) and / or compound (Y) for use.

[0116] Compound (X) is dissolved in a solvent at 298 K in 250,000 L. * mol -1 The invention also relates to compositions, methods, and uses comprising each embodiment described herein, having a stability constant exceeding the value of , wherein the solvent is one or more compounds (Y) each containing an olefin double bond, and / or the solvent is an inert solvent for compound (X) and / or compound (Y), and the stability constant is determined as defined herein.

[0117] In a preferred embodiment, the stability constant is 300,000 L * mol -1 Over, or 350,000L * mol -1 Over, or 400,000L * mol -1 It's incredible.

[0118] In one embodiment, the stability constant is 2,000,000 L * mol -1 It is less than.

[0119] In a preferred embodiment, the stability constant is 1,000,000 L * mol -1 It is less than. [Examples]

[0120] Preparation Examples The complexes used in the following examples can be prepared by known methods, either publicly known, disclosed in the references mentioned in the background art section, or publicly known from Schrock's publications.

[0121] Example 1:

[0122] Dimethyldiallyl malonate [ka] and, [ka] The mixture was stirred in a vial equipped with a perforated septum for ethylene release, without additional solvent, at a temperature of 70 °C for 13 hours with a catalyst loading of 1,000 ppm to obtain 1 more than 99% confirmed by 1H NMR and GC analysis of

Chemical formula

[0123] Example 2

[0124] 1-Decene

Chemical formula

Chemical formula

Chemical formula

[0125] Example 3

[0126] The experiments disclosed in Table 1 below were carried out using Catalyst 2 applicable to

Chemical formula

Table 1

[0127] Example 4

[0128] Table 2 shows a comparison of non-dissociative catalyst 2, 14-electron catalysts 1, 5, and 6, and dissociable complex 4 in the ring-opening metathesis polymerization (ROMP) of DCPD when DCPD and the catalyst are mixed at room temperature. [Table 2] a General: The reaction was carried out in a 30 mL vial sealed with a septum. The initiator was applied in a 0.037 M PhCl stock solution. To improve mixing efficiency, the RIM monomer was added to the initiator stock solution. (In the reverse setting, encapsulation occurred in case 5.) After mixing the RIM monomer and initiator stock solution at room temperature, the mixture was allowed to react without stirring or heating. Due to the exothermic nature and high reaction rate of DCPD ROMP, high-yield ROMP was always accompanied by a rapid temperature rise after initiation. b The start of the reaction was defined as the point at which the reaction mixture becomes non-flowing and the temperature begins to rise rapidly. (The two phenomena typically occur in parallel.) cDetermined by thermogravimetric analysis of the polymer. d Glass transition temperature.

[0129] It is remarkable that the 14 electron catalysts 1, 5, and 6 induce the reaction at room temperature within a very short initiation time, i.e., within the time it takes for the reaction mixture to become non-fluid due to the start of polymerization and for the temperature to begin to rise rapidly above 100°C due to the exothermic reaction.

[0130] When using the dissociative (self-activating) catalyst 4, homogeneous mixing could not be achieved due to the spontaneous reaction and the high reactivity of DCPD. The reaction produced heterogeneous products, likely due to catalyst encapsulation and / or decomposition. The same applies to catalyst 1.

[0131] In contrast to complexes 1, 4, 5, and 6, a prolonged initiation occurred with the non-dissociative complex 2. Complex 2 is non-dissociative at room temperature, meaning the complex is thermodynamically stable, but not bound by theory. However, the inventors of this invention surmise that the observed smooth reaction at room temperature with a prolonged initiation time can be explained by the presence of trace amounts of compound 1 in adduct 2. These trace amounts present in DCPD can initiate the ROMP reaction with the highly reactive olefin. The high exothermic nature of the reaction provides enough heat to heat the composition to a temperature much higher than 50°C, resulting in the near-complete conversion of DCPD.

[0132] Example 5

[0133] Table 3 shows the ROMP reaction of DCPD using a non-dissociative phenanthroline complex. [Table 3] aGeneral: The reaction was carried out in a 30 mL vial sealed with a septum. The initiator was added in a 0.037 M PhCl stock solution. The RIM monomer was added to the initiator stock solution. After mixing the RIM monomer and initiator stock solution at room temperature, the mixture was heated without stirring in an aluminum heating block. b The start of the reaction was defined as the point at which the reaction mixture becomes non-flowing and the temperature begins to rise rapidly, indicated by the vaporization and condensation of residual volatile components within the vial. (These two phenomena typically occur quickly and sequentially.) c Determined by thermogravimetric analysis of the polymer. d Glass transition temperature. (The above compound 3 is identical to compound 2 disclosed by Heppekausen and Furstner, as mentioned in the background art section.)

[0134] Example 6 Table 4 shows the ring-opening metathesis polymerization of "ultrapure" 1,5-cis,cis-cyclooctadiene (COD) promoted by compound 2 in the absence of a Lewis acid activator (compound 2 is identical to compound 3 disclosed by Heppekausen and Huschtner, as mentioned in the background art section). [ka] [Table 4] General: "Ultrapure" COD was completely purified by refluxing over calcium hydride under an argon atmosphere for 24 hours before distillation. The distilled COD was further dried on activated 3A molecular sieves for at least 24 hours before filtration and storage. The reaction was carried out in a 4 mL vial sealed with a septum. 2 was delivered to the vial in 0.037 M PhCl stock solution, to which the substrate was added. No additional solvents were used in either reaction. The vial was heated at 70°C in an aluminum heating block for the specified reaction time. The conversion rate was: 1 This was determined by 1H NMR analysis.

[0135] Example 7

[0136] This embodiment uses Mo(NAr diiPr This provides additional experimental evidence of the thermal activation of )(CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2.

[0137] 1. van't Hoff analysis

[0138] In line with Furstner's findings and claims (doi.org / 10.1002 / anie.201102012 and International Publication No. 2012 / 116695 mentioned in the background technology section), Mo(NAr) is shown in the following scheme. diiPr )(CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 and Mo(NAr diiPr )(CHCMe2Ph)(OC(CF3)2Me)2(1,10-phenanthroline)3 is one of those 1 Based on the 1H NMR spectrum, it was also found that these complexes are non-dissociative at room temperature (298K), which prevented the inventors from determining the thermodynamic stability (stability constant) of these complexes. However, the inventors demonstrated that bipyridine adduct 2 becomes dissociative even at moderately elevated temperatures. This discovery made it possible to experimentally establish the equilibrium constant of 2 at elevated temperatures (above 30 degrees Celsius) and subsequently estimate its stability constant at room temperature. [ka] Scheme. Schrock catalyst Mo(NAr) diiPr )(CHCMe2Ph)(OC(CF3)2Me)21 and its notable 18-electron adduct (Compound 2 is identical to Compound 3 in the Furstner scheme mentioned in the background section, and Compound 3 is identical to Compound 2 in the Furstner scheme mentioned in the background section)

[0139] Mo(NAr diiPrThe equilibrium constant of )(CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 was determined as a function of temperature within the temperature range of 306.60K to 372.95K using an increment of approximately 11K between experiments (entries 2-8, Table 5). The equilibrium constant (or stability constant) at each temperature was determined based on the degree of dissociation of adduct 2, i.e., 1 2 in the 1H NMR sample (0.0101M, toluene-d8) and the corresponding free 14-electron complex Mo(NAr) diiPr The values ​​were determined based on the mole fraction of (CHCMe2Ph)(OC(CF3)2Me)21. The determined lnK values ​​were plotted against the corresponding 1 / T values ​​(Figure 5). The two datasets were obtained from the linear form of the van't Hoff equation (linear form:

number

[0140] Using the linear relationship shown in Figure 5, the stability constant at 25°C / 298K was determined by extrapolation:K トルエン-d8,298K =984609M -1 (Entry 1, Table 5). This value far exceeds the upper limit of the range of stability constants used in the definition of room-temperature dissociable ("self-activating") 18-electron adducts of Schrock catalysts described in British Patent No. 2 537 416, International Publication No. 2021 / 239891, and doi.org / 10.1038 / s42004-021-00503-4. However, as the temperature increases, the stability constant of 2 decreases significantly, reaching 161 M at 372.9 K. -1 It reached (Entry 8, Table 5), which means, 1 Please note that under the conditions of the 1H NMR experiment (0.0101M, toluene-d8, 272.9K), this indicates catalytic activity 1 and more than 50% dissociation of 2 to 2,2'-bipyridine.

[0141] Table 5 below shows, 1 ¹H NMR experiment (0.0101 M, toluene-d8 solution) determines 2 and the corresponding 14-electron complex Mo(NAr). diiPr Based on the molar ratio of (CHCMe2Ph)(OC(CF3)2Me)21, Mo(NAr) is expressed as a function of temperature. diiPr The stability constants for )(CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 are shown. At 298.15K, dissociation is minimal, and the corresponding stability constant was determined by extrapolation. [Table 5] 1. “Thermal activation” Mo(NAr diiPr )(CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 and "self-activating" Mo(NAr diiPr Homocross metathesis of 9-DAME using (CHCMe2Ph)(OC(CF3)2Me)2(4,4-dibromo-2,2'-bipyridine)4.

[0142] Homocross metathesis of methyl 9-decenoate (9-DAME) is performed using "thermal activation" Mo(NAr diiPr )(CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 and "self-activating" Mo(NAr diiPr (CHCMe2Ph)(OC(CF3)2Me)2(4,4-dibromo-2,2'-bipyridine)4 was selected as a model reaction to demonstrate the distinctly different catalytic behavior. Note that 2 is non-dissociative at room temperature and inactive in the absence of a Lewis acid, as stated by Furstner. Furstner detaches the 2,2'-bipyridine ligand from the adduct, thereby activating Mo(NAr diiPr It was argued that in order to liberate )(CHCMe2Ph)(OC(CF3)2Me)21, a Lewis acid must be added to 2. Mo(NAr diiPr)(CHCMe2Ph)(OC(CF3)2Me)2(4,4-dibromo-2,2'-bipyridine)4 was developed by XiMo, structurally modified to dissociate at room temperature, and is active in the absence of Lewis acids. diiPr (CHCMe2Ph)(OC(CF3)2Me)21 can be liberated, and as a result, the olefin metathesis reaction can be catalyzed without the addition of a Lewis acid. As expected from the well-described non-dissociative nature of 2, this adduct did not provide a significant conversion of 9-DAME after 2 hours of reaction at 21°C (Entry 1, Table 6), and the conversion rate remained very low over a 24-hour observation period (7% after 24 hours, Entry 3, Table 6). Under the same conditions, the room-temperature dissociable "self-activating" 4 provided a conversion rate of 28% after 2 hours and 72% after 24 hours (Entry 2 and 4, Table 6), demonstrating a significant difference between the two adducts despite their similar structures and proving the previously devised concept of "self-activating".

[0143] More importantly, the reaction carried out at 70°C fully demonstrates the concept of "thermal activation" as claimed in this application. At the increased temperature, 2 also becomes dissociable and therefore catalytically active, providing performance very similar to that of "self-activating" 4. After 1 hour of reaction, the yields of the homocross-metathesis product were 89% for 2 and 98% for 4, while after 2 hours, the yields were 96% for 2 and 99% for 4 (Entries 5, 6 and 8, 9, Table 6). The similar E:Z ratios indicate that both precatalysts release the same active species 1. It is also noteworthy that both adducts are more catalytically active than the parent complex 1, indicating a role in the chemical protection of the N-heterocyclic Lewis bases 2,2'-bipyridine and 4,4'-dibromo-2,2'-bipyridine (Entries 7, 10 vs 5, 6, 8, 9, Table 6).

[0144] [Table 6] Conditions: 9-DAME: 500 mg / 560 μL, 300 mol ppm catalyst added from 0.0035 M benzene stock solution, vial opened for ethylene release, reaction mixture stirred at a predetermined temperature for a predetermined reaction time. Samples taken from the reaction mixture were analyzed by GC.

Claims

1. A composition capable of performing a metathesis reaction, (X) To form an 18-electron alkylidene compound, (a) 1,10-phenanthroline (optionally substituted) and (b) 2,2'-bipyridine (optionally substituted) A 14-electron shrock alkylidene compound that forms a complex with a bidentate ligand selected from, (Y) Each comprises one or more compounds containing an olefin double bond, The aforementioned composition, (c) MgCl ２ , MgBr ２ , MgI ２ , MnCl ２ , MnBr ２ , MnI ２ , FeCl ３ , AlCl ３ , CuCl ２ , ZnCl ２ , ZnBr ２ , ZnI ２ , Zn(triflate) ２ , or Zn(trifluoroacetate) ２ and does not contain a Lewis acid selected from one or more of the above. (d) The temperature is above 50°C, Preferably, the composition is (e) A composition that does not contain an inert solvent for compound (X) and / or compound (Y).

2. Compound of formula I (X1) 【Chemistry 1】 (In the formula, M is either Mo or W. A is N-R １ Alternatively, selected from O, in the formula, R １ These are C, which has been replaced by any choice. １～１０ It is alkyl or aryl, B is selected from pyrrole, indole, and pyrazole, each substituted by optional choice. C is O-R ２ Selected from, in the formula, R ２ These are C, which are replaced by each of the following options. １～１０ Alkyl or aryl or (C １～１０ Alkyl) ３ Si or (aryl) ３ It is Si, or B is identical to C, and C is O-R ２ Selected from, in the formula, R ２ These are C, which are replaced by each of the following options. １～１０ Alkyl or aryl or (C １～１０ Alkyl) ３ Si or (aryl) ３ It is Si, or Unlike C, B and C are both O-R ２ Selected from, in the formula, R ２ These are C, which are replaced by each of the following options. １～１０ Alkyl or aryl or (C １～１０ Alkyl) ３ Si or (aryl) ３ It is Si, D is 1,10-phenanthroline or substituted 1,10-phenanthroline. R ３ and R ４ These are H and C, independently. １～１０ Alkyl or aryl, C １～１０ Alkyl and aryl groups are optionally substituted, R ３ and R ４ (Containing only one of which is hydrogen) or Compound of formula II (X2) 【Chemistry 2】 (In the formula, M is either Mo or W. A is N-R １ Alternatively, selected from O, in the formula, R １ These are C, which has been replaced by any choice. １～１０ It is alkyl or aryl, B is selected from pyrrole, indole, and pyrazole, each substituted by optional choice. C is O-R ２ Selected from, in the formula, R ２ These are C, which are replaced by each of the following options. １～１０ Alkyl or aryl or (C １～１０ Alkyl) ３ Si or (aryl) ３ It is Si, or B is identical to C, and C is O-R ２ Selected from, in the formula, R ２ These are C, which are replaced by each of the following options. １～１０ Alkyl or aryl or (C １～１０ Alkyl) ３ Si or (aryl) ３ It is Si, or Unlike C, B and C are both O-R ２ Selected from, in the formula, R ２ These are C, which are replaced by each of the following options. １～１０ Alkyl or aryl or (C １～１０ Alkyl) ３ Si or (aryl) ３ It is Si, D is 2,2'-bipyridine or substituted 2,2'-bipyridine. R ３ and R ４ These are H and C, independently. １～１０ Alkyl or aryl, C １～１０ Alkyl and aryl groups are optionally substituted, R ３ and R ４ The composition according to claim 1, comprising (where only one of them is hydrogen).

3. R １ However, C １～１０ Alkyl, C １～１０ Alkoxy, phenyl, halogen, CN, and CF ３ C is independently substituted by one or more of the following: １～１０ The composition according to claim 2, wherein the composition is alkyl or phenyl.

4. B is C １～１０ Alkyl, C １～１０ The composition according to claim 2 or 3, selected from pyrrole, indole, and pyrazole, each independently substituted with one or more alkoxys or phenyls.

5. R ２ However, C was replaced by an arbitrary choice. １～１０ A composition according to any one of claims 2 to 4, selected from alkyl or phenyl.

6. The composition according to any one of claims 1 to 5, wherein the compound (X), or the compound (X1) and the compound (X2), are non-dissociative in the composition at least up to room temperature.

7. C is an electron-withdrawing group, and 1,10-phenanthroline is unsubstituted, or C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more electron-donating groups, or B is identical to C, C is an electron-withdrawing group, and 1,10-phenanthroline is not substituted, or B is identical to C, C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more electron-donating groups, or Unlike C, B and C are both electron-withdrawing groups, and 1,10-phenanthroline is unsubstituted, or Unlike C, B and C are both electron-withdrawing groups, and 1,10-phenanthroline is substituted with one or more electron-donating groups, or B is identical to C, C is an electron-withdrawing group, and 2,2'-bipyridine is not substituted, or B is identical to C, C is an electron-withdrawing group, and 2,2'-bipyridine is substituted with one or more electron-donating groups, or Unlike C, B and C are both electron-withdrawing groups, and 2,2'-bipyridine is unsubstituted, or Unlike C, B and C are both electron-withdrawing groups, and 2,2'-bipyridine is substituted with one or more electron-donating groups. Preferably B is selected from pyrrole, indole, and pyrazole, each substituted by optional choice, and C is O-R ２ Selected from, in the formula, R ２ However, each is halogen or CF ３ C replaced with one or more of the following １～１０ Alkyl or aryl or (C １～１０ Alkyl) ３ Si or (aryl) ３ It is Si, and 1,10-phenanthroline is unsubstituted, or C １～５ Alkyl, C １～５ Alkoxy, -O-(CH ２ ) ｎ 1,10-phenanthroline substituted with one or more selected from -O-(n=1 or 2) and phenyl, or B is the same as C, and C is selected from O-R ２ wherein R ２ is halogen or C ３ alkyl or aryl or (C １～１０ alkyl) １～１０ substituted with one or more of ３ Si or (aryl) ３ Si, 1,10-phenanthroline is unsubstituted or 1,10-phenanthroline is C １～５ alkyl, C １～５ alkoxy, -O-(CH ２ ), ｎ -O-(n = 1 or 2), and phenyl, or B is the same as C, and C is O-R ２ Selected from, in the formula, R ２ However, each is halogen or CF ３ C replaced with one or more of the following １～１０ Alkyl or aryl or (C １～１０ Alkyl) ３ Si or (aryl) ３ It is Si, and the 2,2'-bipyridine is either unsubstituted or C １～５ Alkyl, C １～５ The composition according to any one of claims 2 to 6, wherein it is substituted with one or more selected from alkoxy or phenyl.

8. The composition according to claim 6 or 7, wherein the compound is non-dissociative up to a temperature of 50°C.

9. R ３ and R ４ However, independently, H and C １～１０ Alkyl or aryl, C １～１０ Alkyl or aryl, independently, C １～５ C substituted with one or more alkyl or halogen atoms １～５ Alkyl, C １～５ Substituted with one or more of alkoxy, phenyl, or halogen, In a composition having a temperature of 50°C or lower, the molar ratio of compound (Y), each containing one or more compounds including an olefin double bond, to compound (X), or compound (X1) of formula I, or compound (X2) of formula II, is greater than 2,000, 4,000, 6,000, 8,000, 10,000, 20,000, 30,000, or 40,000, compared to the composition having a temperature above 50°C, or The temperature is greater than 55°C, or greater than 60°C, or greater than 70°C, or greater than 80°C, or greater than 90°C, or greater than 100°C. The composition according to any one of claims 2 to 8, wherein the temperature is in the range of more than 50°C to 140°C, more than 55°C to 130°C, or more than 60°C to 120°C.

10. The aforementioned compound (X) is one of the following compounds 5 to 8 【Transformation 3】 (In the formula, R ２４ = Methyl, phenyl, R ２５ , R ２６ = H, methyl, CF ３ (where Z is selected from methyl, isopropyl, or halogen) or the following compounds III-VI 【Chemistry 4】 Select from one of the following: or the following compounds 【Transformation 5】 (R = Me, Ph, and Ar = 2,6-diisopropylphenyl) 【Transformation 6】 Select from one of the following: Or, 【Transformation 7】 and 【Transformation 8】 A composition according to any one of claims 1 to 9, selected from the following.

11. The compound (X) is dissolved in a solvent at 298 K in 250,000 L. ＊ mol －１ The composition according to any one of claims 1 to 10, having a stability constant exceeding the value of, wherein the solvent is one or more compounds (Y) each containing an olefin double bond, and / or the solvent is an inert solvent for compound (X) and / or compound (Y), and the stability constant is determined as defined herein.

12. The stability constant is 300,000 L ＊ mol －１ Over, or 350,000L ＊ mol －１ Over, or 400,000L ＊ mol －１ A composition according to any one of claims 1 to 11, which is more than [a certain value].

13. A method for preparing the composition according to any one of claims 1 to 12, To provide compound (X) and compound (Y), The provided mixture of compounds is heated to a temperature above 50°C, The composition, MgCl ２ MgBr ２ MgI ２ , MnCl ２ MnBr ２ MnI ２ FeCl ３ AlCl ３ CuCl ２ ZnCl ２ , ZnBr ２ , ZnI ２ Zn (triflate) ２ , or Zn (trifluoroacetate) ２ It does not contain a Lewis acid selected from one or more of the following: Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

14. A method for activating a compound (X) according to any one of claims 1 to 12 in order to initiate an olefin metathesis reaction in a composition comprising one or more compounds (Y), each containing an olefin double bond, The process involves heating a composition containing the aforementioned compound (X) and the aforementioned compound (Y) to a temperature exceeding 50°C. The composition, MgCl ２ MgBr ２ MgI ２ , MnCl ２ MnBr ２ MnI ２ FeCl ３ AlCl ３ CuCl ２ ZnCl ２ , ZnBr ２ , ZnI ２ Zn (triflate) ２ , or Zn (trifluoroacetate) ２ It does not contain a Lewis acid selected from one or more of the following: Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y), or A method for carrying out a metathesis reaction, The method comprises heating a composition containing compound (X) according to any one of claims 1 to 10 and one or more compounds (Y) to a temperature above 50°C. The composition, MgCl ２ MgBr ２ MgI ２ , MnCl ２ MnBr ２ MnI ２ FeCl ３ AlCl ３ CuCl ２ ZnCl ２ , ZnBr ２ , ZnI ２ Zn (triflate) ２ , or Zn (trifluoroacetate) ２ It does not contain a Lewis acid selected from one or more of the following: Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

15. A composition, The compound (X) described in any one of claims 1 to 12 and one or more compounds (Y) are included. The composition, MgCl ２ MgBr ２ MgI ２ , MnCl ２ MnBr ２ MnI ２ FeCl ３ AlCl ３ CuCl ２ ZnCl ２ , ZnBr ２ , ZnI ２ Zn (triflate) ２ , or Zn (trifluoroacetate) ２ It does not contain a Lewis acid selected from one or more of the following: The above composition has a temperature of less than 50°C. Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

16. Use of the composition according to claim 15 in a metathesis reaction, Use of the composition, including heating it to a temperature above 50°C.

17. The use of a compound (X) for initiating a metathesis reaction in a composition comprising one or more compounds (Y) according to any one of claims 1 to 12, The process involves heating a composition containing the aforementioned compound (X) and the aforementioned compound (Y) to a temperature exceeding 50°C. The composition, MgCl ２ MgBr ２ MgI ２ , MnCl ２ MnBr ２ MnI ２ FeCl ３ AlCl ３ CuCl ２ ZnCl ２ , ZnBr ２ , ZnI ２ Zn (triflate) ２ , or Zn (trifluoroacetate) ２ It does not contain a Lewis acid selected from one or more of the following: Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

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