Metathesis compositions comprising air stable imidoalkylene complexes

Abstract

The present invention relates to a composition, each comprising a Srok-alkylene complex bearing a neutral ligand selected from the group consisting of 1, 10-phenanthroline and 2, 2 '-dipyridyl, and one or more compounds comprising an olefinic double bond. When the complex is not dissociated, the complex can be thermally activated to initiate a metathesis reaction in the composition. The invention also relates to a composition comprising a Srok-alkylene complex bearing a neutral 2, 2 '-bipyridine ligand, and one or more compounds comprising an olefinic double bond, in which the complexes are self-activating.

Description

Technical Field

[0001] This invention relates to a composition capable of undergoing a metathesis reaction, comprising an 18-electron molybdenum or tungstenide alkylene complex, and one or more compounds each containing an olefinic double bond, wherein the 18-electron molybdenum or tungstenide alkylene complex is formed from a 14-electron molybdenum or tungstenide alkylene complex with 1,10-phenanthroline or 2,2'-bipyridine as a neutral bidentate ligand. The complex contained in the composition can be activated by heating to initiate a metathesis reaction. The invention also relates to a method for preparing the composition and a method for activating the composition. Background Technology

[0002] Olefin metathesis catalyzed by transition metal catalysts, such as molybdenum or tungsten alkylene catalysts—so-called Schrock catalysts—is one of the most important reactions in organic synthetic chemistry. A valuable known catalyst is the class of Mo(VI) and W(VI) alkylene complexes. The efficacy of this catalyst depends on the type of metal, alkylene group, and ligand. Although such catalysts have proven effective, they are generally unstable in air, making them more difficult to handle and often limiting their applications.

[0003] To improve air stability, WO 2012 / 116695 (Fürstner) recommends stabilizing this catalyst by complexing it with bidentate heterocyclic compounds (e.g., 1,10-phenanthroline and 2,2'-bipyridine). Exemplary 1,10-phenanthroline complexes are as follows, for example, complexes 5 to 8: , Among them, R 24 =Methyl, phenyl; R 25 R 26 =H = methyl, CF3; Z = methyl, isopropyl, halogen.

[0004] However, this air-stable product lacks catalytic activity, while known active forms of catalysts are released upon exposure to Lewis acids (e.g., MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate). The presence of Lewis acids and the formation of adducts between phenanthrene and Lewis acids generally lead to more complex handling of the reaction mixture for separating the reaction products.

[0005] EP 3 268 377 B1 (XiMo AG) discloses a tungsten imine alkylidene catalyst stabilized with 1,10-phenanthroline. The catalyst must be activated by adding 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: .

[0006] The scientific publication of J. Heppekausen and A. Fürstner, “Rendering Schrock-type Molybdenum Alkylidene Complexes Air Stable: User-friendly Precatalysts for Alkene Metathesis,” Angew. Chem. Int. Ed. 2011, 50, pp. 7829–7832 (see: https: / / doi.org / 10.1002 / anie.201102012), discloses that the phenanthroline and bipyridine complexes 2, 3, 5, and 7 of the Schrock catalyst, as determined by NMR spectroscopy, show no signs of partial dissociation (towards 1, 4, or 6) in solvents at room temperature. , Ar = 2,6-diisopropylphenyl.

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

[0008] GB 2 537 416 discloses metathesis catalysts complexed with 2,2'-bipyridine and substituted bipyridine in Examples 3 and 6: ,and .

[0009] These metathesis catalysts can be activated by dissolving in aprotic solvents such as deuterated benzene without the need for the addition of Lewis acids, as the metathesis catalysts spontaneously dissociate (see Examples 10 and 11 of GB 2 537 416). The inventors of GB 2 537 416 refer to the spontaneous release of active catalysts in solvents as "self-activated catalysts".

[0010] This reference further discloses the homo-metathesis reaction of allylbenzene at room temperature without the use of a solvent, catalyzed by the following compounds: .

[0011] The complex is self-activated at room temperature, meaning it dissociates into a 14-electron system and bipyridine. The conversion rate was 54.2% after 16 hours.

[0012] The concept of self-activated bipyridine adducts has also been published in the scientific literature (Gulyás, H. et al., “Air-stable 18-electron adducts of Schrock catalysts with tuned stabilityconstants for spontaneous release of the active species”, Commun. Chem, 4, 71 (2021) (see: https: / / doi.org / 10.1038 / s42004-021-00503-4). This reference discloses the spontaneous metathesis of methyl oleate in benzene at 80 °C, and the ring-closure metathesis of diethyl diallyl malonate in benzene at room temperature, using the following compounds as catalysts: .

[0013] The reference also discloses the ring-opening metathesis polymerization of norbornene in toluene at 25°C, which uses the following compound as a catalyst: .

[0014] WO 2021 / 239891 (Verbio) discloses a Schrock-alkylene complex comprising a phenanthrene ligand D as defined therein: .

[0015] The inventors of WO 2021 / 239891 discovered that, when measured at 298 K and when the complex is dissolved in a solvent, it has the property of [missing information - likely related to a specific concentration] at 5 L*mol. -1 Up to 250,000 L*mol -1 The Schrock-alkylene complex of the above formula, with its stability constant within the range, is air-stable and catalytically active in olefin metathesis without the need for removal of the bidentate ligand by Lewis acid, thus eliminating the formation of corresponding byproducts; i.e., this complex is self-activated. Therefore, this finite stability constant K is used in a chosen solvent to balance between an 18-electron complex containing a bidentate ligand and inactive in olefin metathesis, and a 14-electron complex from which the bidentate ligand has been released through dissociation, wherein the 14-electron complex is catalytically active in olefin metathesis.

[0016] The reference specifically discloses in Example 7 the ethyleneolysis of FAME (fatty acid methyl ester) in benzene at 50°C, using the following compound as a catalyst: , [O-TBS = O-Si(tert-butyl)(methyl)2].

[0017] The above complexes are self-activated. The finite stability constant of the complexes depends on the properties of the solvent. For example, at room temperature (298 K), under similar conditions, the complexes dissociate more readily in CD2Cl2 than in C6D6. In CDCl3, dissociation is even more favorable.

[0018] Purpose of the invention There is a persistent demand in the industry for compositions capable of performing olefin metathesis reactions, wherein the complex used to initiate the reaction in the composition has improved air stability and allows for simplified handling in processes that do not require chemical activation, and there is no risk of premature and uncontrollable reactions due to the high reactivity of the 14-electron complex (parent complex) or the dissociation (self-activation) of the 18-electron adduct when the complex or adduct is mixed with the substrate to be metathesisd at room temperature. Summary of the Invention

[0019] This objective has been achieved using the composition as defined in claim 1, i.e., using a composition capable of undergoing a metathesis reaction, the composition comprising: (X) An 18-electron alkylene compound formed by complexing a 14-electron Schrock alkylene compound with a bidentate ligand selected from: (a) Optionally substituted 1,10-phenanthroline; and (b) Optional substituted 2,2'-bipyridine; as well as (Y) One or more compounds, each containing an alkene double bond; The composition satisfies the following conditions: (c) Does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; and (d) At temperatures above 50°C; In a preferred embodiment, the composition satisfies the following conditions: (e) It does not contain inert solvents used for compound (X) and / or compound (Y).

[0020] The absence of an inert solvent for compound (X) and / or compound (Y) may be beneficial for compositions that produce metathesis products with high melting points, where removing the solvent from the metathesis products would require additional processing.

[0021] The inventors discovered that in a composition of an alkylene compound (X) to be metathesis containing 18-electrons and one or more compounds (Y), each containing an olefinic double bond, the alkylene compound (X) can be modulated to remain undissociated, at least at room temperature. This allows for proper mixing and sufficient processing time without any premature reaction, even if the composition does not contain an inert solvent for compounds (X) and / or (Y). This is significant when the reaction is carried out on an industrial scale, as such a reaction must be controlled.

[0022] The inventors of this invention further discovered that even through 1 ¹H NMR analysis revealed that alkylene compounds without 18 electrons at room temperature dissociate into 14-electron Schrock alkylene compounds and bidentate compounds, but can still initiate metathesis reactions at higher temperatures without chemical activation. The inventors of this invention refer to this effect as thermal activation. Given that it has been assumed until now that only compounds without neutral bidentate ligands are active, this effect is unexpected (see J. Heppekausen and A. Fürstner, as mentioned in the Background section).

[0023] As used herein, the term "non-dissociative complex" refers to a complex that is thermodynamically stable, at least at room temperature. Thermodynamic stability means that the complex (adduct) dissolved or dispersed in a solvent or substrate does not dissociate significantly to the point that it can pass through a solvent or substrate. 1 The extent to which H NMR spectra can be observed.

[0024] This contrasts sharply with the self-activated (dissociated) complexes discussed in the background section, which are clearly thermodynamically unstable because their dissociation can occur through... 1 It can be easily detected by H NMR spectroscopy.

[0025] In a preferred embodiment, compound (X) has a solvent concentration of over 250,000 L*mol at 298 K. -1 The stability constant of the value of , wherein the solvent is one or more compounds (Y) each containing an olefinic double bond, and / or wherein the solvent is an inert solvent used for compounds (X) and / or compounds (Y), the stability constant being determined as defined herein. Attached Figure Description

[0026] As shown in the attached figure: Figure 1 The applicant's complex 1 H NMR spectrum, , As mentioned in the background section by Heppekausen and Fürstner, this complex is at room temperature (C6D5CD3, 298K, 0.01 M); Figure 2 The compound at 70°C 1 H NMR spectrum; Figure 3 The compound at 95°C 1 H NMR spectrum; Figure 4 The compound was obtained after the sample was cooled from 95°C to room temperature. 1 H NMR spectrum; and Figure 5 Mo(NAr diiPr Temperature dependence of the stability constant of (CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine). Detailed Implementation

[0027] The composition according to the invention This invention relates to a composition capable of undergoing a metathesis reaction, the composition comprising: (X) An 18-electron alkylene compound formed by complexing a 14-electron Schrock alkylene compound with a bidentate ligand selected from: (a) Optionally substituted 1,10-phenanthroline; and (b) Optional substituted 2,2'-bipyridine; as well as (Y) One or more compounds, each containing an alkene double bond; The composition satisfies the following conditions: (c) Does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate or zinc trifluoroacetate; (d) At temperatures above 50°C; In a preferred embodiment, the composition does not contain: (e) Inert solvents used for compound (X) and / or compound (Y).

[0028] In one embodiment, the present invention relates to a composition comprising: Compounds of formula (X1), , I (Y) One or more compounds, each containing an alkene double bond; in, M is Mo or W; A is selected from NR 1 Or O, where R 1 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl; B is selected from pyrrole, indole, and pyrazole, which are substituted respectively; and C is selected from OR 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B and C are the same, where C is selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B differs from C, where both B and C are selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; (a) D is 1,10-phenanthroline or a substituted 1,10-phenanthroline; R 3 and R 4 H and C independently 1-10 Alkyl or aryl, optionally substituted C 1-10 Alkyl and aryl; and wherein, R 3 and R 4 Only one of them is hydrogen; The composition satisfies the following conditions: (c) Does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate or zinc trifluoroacetate; (d) At temperatures above 50°C; In a preferred embodiment, the composition satisfies the following conditions: (e) It does not contain inert solvents used for compound (X) and / or compound (Y).

[0029] In another embodiment, the present invention relates to a composition comprising: Compounds of formula (X2) II , II (Y) One or more compounds, each containing an alkene double bond; in, M is Mo or W; A is selected from NR 1 Or O, where R 1 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl; B is selected from pyrrole, indole, and pyrazole, which are substituted respectively; and C is selected from OR 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B and C are the same, where C is selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B differs from C, where both B and C are selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; (b) D is 2,2'-bipyridine or a substituted 2,2'-bipyridine; R 3 and R 4 H and C independently 1-10 Alkyl or aryl, optionally substituted C 1-10 Alkyl and aryl; and wherein, R 3 and R 4 Only one of them is hydrogen.

[0030] The composition satisfies the following conditions: (c) Does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate or zinc trifluoroacetate; (d) At temperatures above 50°C.

[0031] In a preferred embodiment, the composition satisfies the following conditions: (e) It does not contain inert solvents used for compound (X) and / or compound (Y).

[0032] According to the present invention, M is Mo or W.

[0033] In one implementation, M is W.

[0034] In another implementation, M is Mo.

[0035] According to the present invention, A is selected from NR 1 Or O, where R 1 It is an alkyl group, preferably, and the C groups are optionally substituted. 1-10 Alkyl or aryl.

[0036] In the preferred embodiment, A is NR 1 , where R 1 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl.

[0037] As used in this article, the term "alkyl or C" 1-10 "alkyl", for example, is used to define R 1 The term "alkyl or C" 1-10 "Alkyl" includes straight-chain alkyl, branched alkyl, cyclic alkyl, and alicyclic alkyl. Preferred C 1-10 Alkyl is C 1-5 Alkyl group. In another embodiment, C 4-10 Alkyl groups are preferred.

[0038] In one embodiment, alkyl, for example R 1 It is tert-butyl or 1-adamantyl.

[0039] As used in this article, the term "aryl" is used, for example, to define R. 1 The term "aryl" includes phenyl, naphthyl, anthracene, and phenanthrene groups, which are optionally substituted.

[0040] Suitable substituents can be selected from C 1-10 Alkyl, C 1-10 One or more of alkoxy, phenyl, halogen, CN, and CF3.

[0041] Phenyl is preferred as an aryl group.

[0042] In one implementation, R 1 They are independently controlled by C 1-10 Alkyl, C 1-10 One or more substituted C atoms selected from alkoxy, phenyl, halogen, CN, and CF3 1-10 Alkyl or phenyl.

[0043] According to one embodiment of the invention, B is selected from pyrrole, indole, and pyrazole, which are optionally substituted.

[0044] In one implementation, B is selected from C, which are independently selected from C. 1-5 Alkyl, C 1-5 One or more substituted pyrroles, indoles, and pyrazoles of alkoxy or phenyl groups.

[0045] According to the present invention, C is selected from OR 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 Alkyl)3Si or (aryl)3Si.

[0046] In the preferred embodiment, R 2 It is an electron-withdrawing group. The term "electron-withdrawing group" has the generally accepted meaning in this field.

[0047] In one implementation, R 2 It is a phenyl group that is substituted with -(CH2)4- to form an annulated ring with a phenyl group, or a phenyl group that is substituted with -(CH=CH-CH=CH)- to form an annulated ring with a phenyl group. In this paper, the annulated ring may be substituted with O-methylalkyl groups.

[0048] The term "silyl" can refer to any silyl group that forms a covalent bond between silicon and oxygen. Suitable silyl groups are, for example, tert-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), and triphenylsilyl.

[0049] Similarly, the term (C) 1-10 Alkyl)3Si or (aryl)3Si contains the silyl group defined above.

[0050] According to the present invention, D is a neutral bidentate ligand.

[0051] In the compound (X1) of formula I, the neutral ligand is (a) 1,10-phenanthroline or a substituted 1,10-phenanthroline. Both N atoms of the phenanthroline skeleton are bonded to M, thereby forming a bidentate ligand and thus an 18-electron alkylene compound.

[0052] 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 its commonly accepted meaning in the art.

[0053] In one embodiment, 1,10-phenanthroline is independently reacted with C 1-5 Alkyl, C 1-5 Alkyl group, -O-(CH2) n One or more substitutions of -O- and phenyl, n=1 or 2. These groups represent electron-donating groups in the sense of this invention.

[0054] Commercially available substituted 1,10-phenanthroline 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.

[0055] In a further preferred embodiment, C is an electron-withdrawing group, and 1,10-phenanthroline is unsubstituted.

[0056] In a further preferred embodiment, C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more electron-donating groups as defined above.

[0057] In a further preferred embodiment, B is the same as C, wherein C is an electron-withdrawing group and 1,10-phenanthroline is unsubstituted.

[0058] In a further preferred embodiment, B is the same as C, wherein C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more of the electron-donating groups defined above.

[0059] In a further 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 electron-donating groups as defined above.

[0060] In one embodiment, B is selected from pyrrole, indole, and pyrazole, which are optionally substituted, respectively, and C is selected from OR 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si, or (C 1-10 The alkyl)3Si or (aryl)3Si is selected from tert-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), and triphenylsilyl; and 1,10-phenanthroline is unsubstituted or selected from C 1-5 Alkyl, C 1-5 Alkyl group, -O-(CH2) n One or more substitutions in -O- and phenyl, n=1 or 2.

[0061] In one embodiment, B is selected from pyrrole, indole, and pyrazole, which are optionally substituted, respectively, and C is selected from (CF3)3CO-, (CCl3)(CF3)2CO-, (C6H5)(CF3)2CO-, (CH3)(CF3)2CO-, ClC6H4O-, Cl2C6H3O-, Cl3C6H2O-, BrC6H4O-, Br2C6H3O-, Br3C6H4O-, CF3C6H4O-, (CF3)2C6H3O-, Cl(CF3)C6H3O-, tert-butyldimethylsiloxy (TBSO, TBDMSO), trimethylsiloxy (TMSO), triethylsiloxy (TESO), triisopropylsiloxy (TIPS) )O, tert-butyldiphenylsiloxy (TBDPSO), and triphenylsiloxy; and 1,10-phenanthroline is 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-m-dioxane.

[0062] In one implementation, B is the same as C, where C is selected from OR 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or (C 1-10 (alkyl)3Si or (aryl)3Si is tert-butyldimethylsilyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldiphenylsilyl, or triphenylsilyl; and 1,10-phenanthroline is unsubstituted or selected from C 1-5 Alkyl, C 1-5 Alkyl group, -O-(CH2) n One or more substitutions in -O- and phenyl, n=1 or 2.

[0063] In another embodiment, B is the same as C, wherein 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-, tert-butyldimethylsiloxy, trimethylsiloxy, triethylsiloxy, triisopropylsiloxy tert-butyldiphenylsiloxy and triphenylsiloxy; and 1,10-phenanthroline is 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-m-dioxane.

[0064] In another implementation, B differs from C, where both B and C are selected from OR. 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 1-10 Alkyl or aryl or (C 1-10alkyl)3Si or (aryl)3Si; or (C 1-10 (alkyl)3Si or (aryl)3Si is tert-butyldimethylsilyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldiphenylsilyl, or triphenylsilyl; and 1,10-phenanthroline is unsubstituted or selected from C 1-5 Alkyl, C 1-5 Alkyl group, -O-(CH2) n One or more substitutions in -O- and phenyl, n=1 or 2.

[0065] In another embodiment, B differs from C, wherein 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-, tert-butyldimethylsiloxy, trimethylsiloxy, triethylsiloxy, triisopropylsilane. Oxygen, tert-butyldiphenylsiloxy, and triphenylsiloxy; and 1,10-phenanthroline is 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-m-dioxane.

[0066] The inventors of this invention have discovered that such a complex of formula I is non-dissociable in the composition according to the invention, at least at room temperature.

[0067] In compound (X1) of formula II, the neutral ligand is (b) 2,2'-bipyridine or a substituted 2,2'-bipyridine. Both N atoms of the bipyridine skeleton are bonded to M, thereby forming a bidentate ligand and thus an 18-electron alkylene compound.

[0068] In a preferred embodiment, 2,2'-bipyridine is independently reacted with C 1-5 Alkyl, C 1-5One or more substitutions of alkoxy or phenyl groups. These groups represent electron-donating groups in the sense of this invention.

[0069] For example, commercially available bipyridines having electron-donating groups are 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.

[0070] In a further preferred embodiment, B is the same as C, wherein 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.

[0071] In a further preferred embodiment, B is different from C, but both B and C are electron-withdrawing groups, and D is 2,2'-bipyridine or 2,2'-bipyridine substituted with one or more electron-donating groups as defined above.

[0072] In a preferred embodiment, B is the same as C, where C is selected from OR 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or (C 1-10 The alkyl)3Si or (aryl)3Si is selected from tert-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), and triphenylsilyl; and the 2,2'-bipyridine is unsubstituted or selected from C 1-5 Alkyl, C 1-5 One or more substituted 2,2'-bipyridines of alkoxy or phenyl groups.

[0073] In a preferred embodiment, B is the same as C, wherein 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-, or tert-butyldimethylsiloxy, trimethylsiloxy, triethylsiloxy, triisopropylsiloxy, tert-butyldiphenylsiloxy, and triphenylsiloxy; 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.

[0074] In a further preferred embodiment, B differs from C, wherein both B and C are selected from OR 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 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 tert-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), and triphenylsilyl; and D is selected from 2,2'-bipyridine or selected from C 1-5 Alkyl, C 1-5 One or more substituted 2,2'-bipyridines of alkoxy and phenyl groups.

[0075] In a further preferred embodiment, B differs from C, wherein 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-, CF3C6H4 O-, (CF3)2C6H3O-, Cl(CF3)C6H3O-, or tert-butyldimethylsiloxy, trimethylsiloxy, triethylsiloxy, triisopropylsiloxy, tert-butyldiphenylsiloxy, and triphenylsiloxy; 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.

[0076] The inventors of this invention have discovered that such complexes of formula II are generally non-dissociable in compositions according to the invention at room temperature or at least at room temperature.

[0077] Therefore, in a preferred embodiment, the composition according to the invention requires that the compound of formula I (X1) and the compound of formula II (X2) contained therein be non-dissociated in the composition at least at room temperature.

[0078] In one embodiment, the compound of formula I (X1) or the compound of formula II (X2) in the composition is referred to as non-dissociative, provided that their stability constant measured at 298 K exceeds 250,000 L*mol. -1 The value is sufficient. A further preferred range, measured at 298 K, is greater than 300,000 L*mol. -1 or greater than 350,000 L*mol -1 or greater than 400,000 L*mol -1 The stability constant can be determined using known methods employing the law of mass action. See WO 2021 / 239891, as mentioned in the background section.

[0079] Complexes with an almost infinite stability constant K, i.e., complexes with an excessively high stability constant in a predetermined solvent such as compound (X2), are too stable to release the active form from it. This applies to complexes known from the prior art, as mentioned in the Background section, that require the assistance of Lewis acids to remove bidentate ligands.

[0080] In another embodiment, the non-dissociative properties of the compound of formula I (X1) or the compound of formula II (X2) can be achieved through... 1 This can be verified by 1H NMR spectroscopy, which is evident in the prior art (J. Heppekausen and A. Fürstner) mentioned in the background section.

[0081] Figures 1 to 3 of 1 1H NMR spectra show that when heated, the phenanthroline complexes from J. Heppekausen and A. Fürstner, as mentioned in the background section, exhibit [behavior / property characteristics]. , The complex remained undissociated at temperatures up to 95°C. Upon cooling, Figure 4 The spectrum and Figure 1 The spectra are the same. The shifts in the aliphatic regions (isopropyl, methyl) are due to temperature effects.

[0082] Possible dissociation can be detected by the chemical shift of alkylene protons; the chemical shifts of 18-electron and 14-electron complexes are different. It can also be detected by... 1 ¹H NMR spectroscopy quantitatively records possible (partial) dissociations. The corresponding methods are known in the art.

[0083] According to the present invention, when the temperature is above 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 to form an activated 14-electron complex from the 18-electron complex. Instead, the complex of Formula I or Formula II is thermally activated, i.e., chemical activation is not required. Surprisingly, even though NMR analysis shows no dissociation at higher temperatures above 50°C, the thermally activated catalyst of Formula I or Formula II initiates the metathesis reaction. Given that it has been assumed until now that only compounds without neutral bidentate ligands are active, this effect is unexpected (see J. Heppekausen and A. Fürstner, as mentioned in the Background section).

[0084] WO2021 / 239891 provides guidance on the custom synthesis of non-dissociative complexes. This document discloses how the appropriate selection of ligands in the complex can affect the stability constant of the complex. The inventors have found that, through substitution, particularly with respect to at least D (1,10-phenanthroline and substituted 1,10-phenanthroline) or other ligands B and C such as alkoxide, aryloxide, or D and C, the stability constant K in solvent relative to a neutral bidentate ligand, as measured at 298 K, can be adjusted to 5 L*mol when the complex is dissolved in a solvent to release the active form from the 18-electron complex, i.e., the 14-electron complex. -1 Up to 250,000 L*mol -1 Within the range.

[0085] WO2021 / 239891 discloses in one embodiment that, compared to a complex of 1,10-phenanthroline having the same substitution pattern in aspects A, B, and C but wherein the bidentate ligand is unsubstituted, the 1,10-phenanthroline is substituted with one or more electron-donating groups to increase the stability constant. In another embodiment, compared to a complex of 1,10-phenanthroline having the same substitution pattern in aspects A, B, and C but wherein the bidentate ligand is unsubstituted, the 1,10-phenanthroline is substituted with one or more electron-withdrawing groups to decrease the stability constant.

[0086] In another embodiment, the spatial volume (i.e., the spatial expansion of residue C) is increased compared to complexes having the same substitution pattern in A, B, and D, in order to decrease the stability constant. In another embodiment, the spatial volume (i.e., the spatial expansion of residue C) is decreased compared to complexes having the same substitution pattern in A, B, and D, in order to increase the stability constant.

[0087] Therefore, the methods defined in WO2021 / 239891 can also be used to prepare non-dissociated complexes of the compounds defined in Formula I and Formula II of this invention.

[0088] The content of WO2021 / 239891 is incorporated into this article in its entirety by reference.

[0089] As used herein, the term "room temperature" is defined as a temperature up to 25°C, preferably, as a temperature between 15°C and 25°C. The term "room temperature" is used synonymously with the term "ambient temperature".

[0090] The term “at least up to room temperature” used in this document for compounds of formula I (X1) and formula II (X2) includes temperatures above 25°C. Therefore, this term can be used synonymously with the term “at least up to room temperature and above”.

[0091] In one embodiment, the compound of formula I (X1) or the compound of formula II (X2) is non-dissociable at temperatures up to at least 50°C, or 60°C, or 70°C, or 80°C, or 100°C, or 120°C, or higher.

[0092] In one implementation, R 3 and R 4 H and C independently 1-10 alkyl or aryl, wherein C 1-10 The alkyl or aryl group is independently substituted by one or more of the following groups: C 1-5 Alkyl groups, C substituted with one or more halogens 1-5 Alkyl, C 1-5 Alkoxy, phenyl, halogen.

[0093] In one embodiment, the composition according to the invention is at a temperature 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 is in the range of above 50°C to 140°C, or above 55°C to 130°C, or above 60°C to 120°C.

[0094] According to the present invention, the composition does not contain Lewis acids.

[0095] In one embodiment, compared to compositions at temperatures above 50°C, in compositions at temperatures of 50°C or below, the molar ratio of compound (Y) comprising one or more compounds containing olefinic double bonds to compound (X1) of formula I or compound (X2) of formula II is greater than 2000, or 4000, or 6000, or 8000, or 10000, or 20000, or 30000, or 40000.

[0096] According to a preferred embodiment, the composition does not contain an inert solvent for compound (X) and / or compound (Y). However, as used herein, this term does not exclude the use of a small amount of inert solvent for treating compound (X1) or compound (X2). Therefore, the term "wherein the composition does not contain an inert solvent for compound (X) and / or compound (Y)" as used herein includes an inert solvent, such as benzene, or toluene, or chlorobenzene, or a hydrocarbon, which may be present in the composition, wherein the molar ratio of one or more compounds, each comprising an olefinic double bond, to the inert solvent is greater than 200, or greater than 500, or greater than 1000, or greater than 2000.

[0097] Therefore, in a preferred embodiment, compound (Y) is a solvent, wherein the solvent does not contain another solvent, such as an inert solvent, such as benzene, toluene, chlorobenzene, or hydrocarbon.

[0098] In one embodiment, the compound of formula I is selected from one of the following compounds 5 to 8: , Among them, R 24 =Methyl, phenyl; R 25 R 26 =H, methyl, CF3; Z = methyl, isopropyl, halogen; or The compound of formula I is selected from one of the following compounds III to VI: ;or The compounds of formula I are selected from one of the following compounds: , R = Me, Ph; Ar = 2,6-diisopropylphenyl; ;or Among them, the compounds of formula II are selected from: ,and .

[0099] Method for preparing the composition according to the present invention The present invention also relates to a method for preparing a composition according to the invention, the method comprising: Provide compound (X) (or compound (X1) of formula I or compound (X2) of formula II) and one or more compounds (Y); Heat the mixture of the provided compounds to a temperature above 50°C; in, The composition does not contain one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

[0100] Thermal activation method The present invention also relates to a method for activating a compound (X) (or (X1) of Formula I or (X2) of Formula II as defined above) for initiating an olefin metathesis reaction in a composition comprising one or more compounds (Y), the method comprising: The composition containing compound (X) (or compound (X1) and compound (X2)) and compound (Y) is heated to a temperature above 50°C; in, The composition does not contain one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y); The present invention also relates to a method for carrying out a metathesis reaction, the method comprising: The composition comprising compound (X) (or compound (X1) of formula I or compound (X2) of formula II) and one or more compounds (Y) is heated to a temperature above 50°C. in, The composition does not contain one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

[0101] Further topics The present invention also relates to a composition comprising: The compound (X) defined above (or compound (X1) of formula I or compound (X2) of formula II); and One or more compounds (Y) each containing an olefinic double bond; The composition does not contain one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate. The temperature of the composition is below 50°C; Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

[0102] This invention also relates to the use of the composition in metathesis reactions, including: Heat the composition to a temperature above 50°C.

[0103] The present invention also relates to the use of compound (X) (or compound (X1) of formula I as defined above or compound (X2) of formula II) in initiating a metathesis reaction in one or more compounds (Y), each comprising an olefinic double bond, the uses including: The composition containing compound (X) (or compound (X1) and compound (X2)) and compound (Y) is heated to a temperature above 50°C; in, The composition does not contain one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; Preferably, the composition does not contain an inert solvent for compound (X) and / or compound (Y).

[0104] The compositions according to the present invention can be used in all types of olefin metathesis reactions.

[0105] In one embodiment, in the composition according to the invention, one or more compounds, each comprising an olefinic double bond, are selected such that a cross-metathesis reaction (CM) is carried out, the cross-metathesis reaction (CM) comprising self-metathesis [(homo)-cross-metathesis (HCM)].

[0106] In another embodiment, in the composition according to the invention, one or more compounds, each containing an olefinic double bond, are selected such that a ring-closed metathesis reaction (RCM) is carried out.

[0107] In another embodiment, in the composition according to the invention, one or more compounds, each containing an olefinic double bond, are selected such that a ring-opening metathesis reaction (ROM) is carried out.

[0108] In another embodiment, in the composition according to the invention, one or more compounds, each containing an olefinic double bond, are selected such that ring-opening metathesis polymerization (ROMP) is carried out.

[0109] In another embodiment, in the composition according to the invention, one or more compounds, each containing an olefinic double bond, are selected such that an acyclic diene metathesis reaction (ADMET) is carried out.

[0110] This invention also relates to the following items: 1. A composition capable of undergoing a metathesis reaction, the composition comprising: (X) An 18-electron alkylene compound formed by complexing a 14-electron Schrock alkylene compound with a bidentate ligand selected from: (a) Optionally substituted 1,10-phenanthroline; and (b) Optional substituted 2,2'-bipyridine; as well as (Y) One or more compounds, each containing an alkene double bond; The composition satisfies the following conditions: (c) Does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate or zinc trifluoroacetate; (d) At temperatures above 50°C; (e) Contains an inert solvent for compound (X) and / or compound (Y).

[0111] 2. The composition according to item 1, wherein the composition comprises: Compounds of formula (X1), , I in, M is Mo or W; A is selected from NR 1 Or O, where R 1 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl; B is selected from pyrrole, indole, and pyrazole, which are substituted respectively; and C is selected from OR 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B and C are the same, where C is selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B differs from C, where both B and C are selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; D is 1,10-phenanthroline or substituted 1,10-phenanthroline; R 3 and R 4 H and C independently 1-10 Alkyl or aryl, optionally substituted C 1-10 Alkyl and aryl; and wherein, R 3 and R 4 Only one of them is hydrogen; or include Compounds of formula (X2) II , II in, M is Mo or W; A is selected from NR 1 Or O, where R 1 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl; B is selected from pyrrole, indole, and pyrazole, which are substituted respectively; and C is selected from OR 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B and C are the same, where C is selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B differs from C, where both B and C are selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; D is 2,2'-bipyridine or substituted 2,2'-bipyridine; R 3 and R 4 H and C independently 1-10 Alkyl or aryl, optionally substituted C 1-10 Alkyl and aryl; and wherein, R 3 and R 4 Only one of them is hydrogen.

[0112] 3. According to the composition of Project 2, wherein R 1 They are independently controlled by C 1-10 Alkyl, C 1-10 One or more substituted C atoms selected from alkoxy, phenyl, halogen, CN, and CF3 1-10 Alkyl or phenyl.

[0113] 4. A composition according to any one of items 2 to 3, wherein B is selected from C, which is independently reacted with C. 1-10 Alkyl, C 1-10One or more substituted pyrroles, indoles, and pyrazoles of alkoxy or phenyl groups.

[0114] 5. A composition according to any one of items 2 to 4, wherein R 2 Selected from the C that is arbitrarily replaced 1-10 Alkyl or phenyl.

[0115] 6. A composition according to any one of items 1 to 5, wherein compound (X) or compound (X1) and compound (X2) are non-dissociated in the composition at at least the highest room temperature.

[0116] 7. A composition according to any one of items 2 to 6, wherein 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 the same as C, where C is an electron-withdrawing group and 1,10-phenanthroline is unsubstituted; or B is the same as C, wherein C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more electron-donating groups; or B differs from C in that both B and C are electron-withdrawing groups, and 1,10-phenanthroline is unsubstituted; or B differs from C in that both B and C are electron-withdrawing groups, and 1,10-phenanthroline is substituted by one or more electron-donating groups; or B is the same as C, where C is an electron-withdrawing group and 2,2'-bipyridine is unsubstituted; or B is the same as C, wherein C is an electron-withdrawing group, and 2,2'-bipyridine is substituted by one or more electron-donating groups; or B differs from C in that both B and C are electron-withdrawing groups, and 2,2'-bipyridine is unsubstituted; or B differs from C, where both B and C are electron-withdrawing groups, and 2,2'-bipyridine is substituted by one or more electron-donating groups; Preferably, wherein, B is selected from pyrrole, indole, and pyrazole, which are substituted respectively, and C is selected from OR 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B and C are the same, where C is selected from OR. 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3.1-10 Alkyl or aryl or (C 1-10 (alkyl)3Si or (aryl)3Si; and 1,10-phenanthroline is unsubstituted or selected from C 1-5 Alkyl, C 1-5 Alkyl group, -O-(CH2) n One or more substituted 1,10-phenanthrolines of -O- and phenyl groups, n=1 or 2; or B and C are the same, where C is selected from OR. 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 1-10 Alkyl or aryl or (C 1-10 (alkyl)3Si or (aryl)3Si; and 2,2'-bipyridine is unsubstituted or selected from C 1-5 Alkyl, C 1-5 One or more substitutions of alkoxy or phenyl.

[0117] 8. A composition according to any one of items 1 or 7, wherein compound (X) (or compound (X1) and compound (X2)) is non-dissociative at temperatures up to 50°C.

[0118] 9. A composition according to any one of items 2 to 8, wherein R 3 and R 4 H and C independently 1-10 alkyl or aryl, wherein C 1-10 The alkyl or aryl group is independently substituted by one or more of the following groups: C 1-5 Alkyl groups, C substituted with one or more halogens 1-5 Alkyl, C 1-5 Alkoxy, phenyl, halogen.

[0119] 10. A composition according to any one of items 1 to 9, wherein, compared with a composition at a temperature above 50°C, in a composition at a temperature of 50°C or below, the molar ratio of compound (Y), which comprises one or more compounds each comprising an olefinic double bond, to compound (X), or compound of formula I (X1), or compound of formula II (X2), is greater than 2000, or 4000, or 6000, or 8000, or 10000, or 20000, or 30000, or 40000.

[0120] 11. A composition according to any one of items 1 to 10, wherein the temperature is higher than 55°C, or higher than 60°C, or higher than 70°C, or higher than 80°C, or higher than 90°C, or higher than 100°C; or The temperature ranges from 50°C to 140°C, from 55°C to 130°C, or from 60°C to 120°C.

[0121] 12. A composition according to any one of items 1 to 11, wherein compound (X) is selected from one of compounds 5 to 8: , Among them, R 24 =Methyl, phenyl; R 25 R 26 =H, methyl, CF3; Z = methyl, isopropyl, halogen; or Compound (X) is selected from one of the following compounds III through VI: ;or Compound (X) is selected from one of the following compounds: , R = Me, Ph; Ar = 2,6-diisopropylphenyl; ;or Compound (X) is selected from: ,and .

[0122] 13. A method for preparing a composition as defined in any one of items 1 to 12, the method comprising: Provide compound (X) and compound (Y); Heat the mixture of the provided compounds to a temperature above 50°C; in, The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate or zinc trifluoroacetate; Preferably, the composition comprises an inert solvent for compound (X) and / or compound (Y).

[0123] 14. A method for activating a compound (X) as defined in any one of items 1 to 12, for initiating an olefin metathesis reaction in a composition comprising one or more compounds (Y), each comprising an olefinic double bond, the method comprising: The composition containing compound (X) and compound (Y) is heated to a temperature above 50°C; in, The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; and The composition contains an inert solvent for compound (X) and / or compound (Y).

[0124] 15. A method for carrying out a double displacement reaction, the method comprising: The composition comprising a compound (X) as defined in any one of items 1 to 12 and one or more compounds (Y) is heated to a temperature above 50°C. in, The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; and The composition contains an inert solvent for compound (X) and / or compound (Y).

[0125] 16. A composition comprising: According to any one of items 1 to 12, there is a compound (X) and one or more compounds (Y); The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate or zinc trifluoroacetate; The temperature of the composition is below 50°C; and The composition contains an inert solvent for compound (X) and / or compound (Y).

[0126] 17. Use of the composition in metathesis reactions as defined in Item 16, including: Heat the composition to a temperature above 50°C.

[0127] The composition contains an inert solvent for compound (X) and / or compound (Y).

[0128] 18. Use of compound (X) to initiate a metathesis reaction in a composition comprising one or more compounds (Y) as defined in any one of items 1 to 12, the use including: The composition containing compound (X) and compound (Y) is heated to a temperature above 50°C; in, The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate or zinc trifluoroacetate; The composition contains an inert solvent for compound (X) and / or compound (Y).

[0129] The present invention also relates to compositions, methods, and uses comprising the corresponding embodiments described herein, wherein compound (X) has a concentration of more than 250,000 L*mol in a solvent at 298 K. -1 The stability constant of the value, wherein the solvent is one or more compounds (Y) each containing an olefinic double bond, and / or wherein the solvent is an inert solvent used for compounds (X) and / or compounds (Y), the stability constant being determined as defined in the specification.

[0130] In the preferred embodiment, the stability constant is greater than 300,000 L*mol. -1 or greater than 350,000 L*mol -1 or greater than 400,000 L*mol -1 .

[0131] In one implementation, the stability constant is less than 2,000,000 L*mol. -1 .

[0132] In a preferred embodiment, the stability constant is less than 1,000,000 L*mol. -1 .

[0133] example Preparation Examples The complexes used in the following examples are known or can be prepared by known methods disclosed in the references mentioned in the Background section or by known methods known from Schrock publications.

[0134] Example 1: In vials equipped with perforated diaphragms for ethylene release, a mixture of dimethyl diallyl malonate is released without the need for additional solvents. ,and , The mixture was stirred at 70°C with a catalyst loading of 1000 ppm for 13 hours, as if... 1 As confirmed by 1H NMR and GC analysis, the following compounds produced greater than 99% of the total: .

[0135] Example 2 In vials equipped with perforated diaphragms for ethylene release, a mixture of 1-decene is released without the need for additional solvents. ,and , The mixture was stirred at 70°C with a catalyst loading of 1000 ppm for 13 hours, as if... 1 The following compounds, confirmed by 1H NMR and GC analysis, produce 85% (cis / trans mixture): .

[0136] Example 3 The experiments disclosed in Table 1 below were performed using catalyst 2 as shown below: .

[0137] Item 4 indicates that the catalyst is inactive at room temperature, while it can be activated at higher temperatures.

[0138]

[0139] Overview: The reaction was carried out in 4-mL vials sealed with a septum. A magnetic stir bar was provided to the vial containing 1-decene and DEDAM, and the septum was punctured with a needle to release ethylene. 2 was delivered to the pure substrate in a 0.037 M PhCl stock solution. No additional solvent was used in any reaction. The vial was heated at 70 °C in an aluminum heating block for the given reaction time. The reaction mixture of 1-decene and DEDAM was stirred while polymerization was carried out without stirring. After the reaction was complete, the cyclooctadiene ROMP was analyzed by ¹H NMR, while the reaction mixture of 1-decene and DEDAM was analyzed by ¹H NMR and GC-MS. In the case of 1-decene, the conversion was 69% as determined by ¹H NMR and 85% as determined by (uncalibrated) GC-MS. The metathesis and polymerization of the cyclic olefin produced the expected mixture of cis and trans isomers.

[0140] Example 4 Table 2 shows a comparison of the non-dissociated catalyst 2 with the 14-electron catalysts 1, 5 and 6, and the dissociated complex 4 in the ring-opening metathesis polymerization (ROMP) of DCPD when DCPD and catalysts are mixed at room temperature (RIM = reaction injection molding).

[0141] Table 2

[0142]

[0143] a Overview: The reaction was carried out in 30-mL vials sealed with a septum. The initiator was added to a 0.037 M PhCl stock solution. The RIM monomer was added to the initiator stock solution to improve mixing efficiency. (In case 5, if the order is reversed, encapsulation will occur.) After mixing the RIM monomer and the 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 yields of ROMP are always accompanied by a rapid temperature rise after the initial time. b The onset time is defined as the point at which the reaction mixture becomes non-fluid and the temperature begins to rise sharply. (These two phenomena usually occur in parallel.) c The determination was made by thermogravimetric analysis of the polymer. d Glass transition temperature.

[0144] Surprisingly, the 14-electron catalysts 1, 5, and 6 initiate the reaction at room temperature within a very short onset time. That is, when the reaction mixture becomes non-fluid due to the start of polymerization and the temperature begins to rise sharply to a temperature well above 100°C due to the exothermic reaction, the 14-electron catalysts 1, 5, and 6 initiate the reaction at room temperature within a very short onset time.

[0145] For the dissociated (self-activated) catalyst 4, homogeneous mixing cannot be achieved due to the spontaneous reaction and the high reactivity of DCPD. The reaction produces heterogeneous products, which may be due to catalyst encapsulation and / or degradation. The same applies to catalyst 1.

[0146] In contrast to complexes 1, 4, 5, and 6, the non-dissociated complex 2 results in an extended onset time. Although complex 2 is non-dissociated at room temperature, i.e., the complex is thermodynamically stable, the inventors of this invention, not bound by theory, hypothesize that the stationary reaction with an extended onset time observed at room temperature can be explained by the presence of trace amounts of compound 1 in adduct 2. These trace amounts present in DCPD can initiate a ROMP reaction with a very reactive olefin. The highly exothermic nature of this reaction provides sufficient heat to heat the composition to temperatures well above 50°C, resulting in the near-complete conversion of DCPD.

[0147] Example 5 Table 3 shows the ROMP reaction of DCPD using non-dissociated phenanthroline complexes:

[0148] aOverview: The reaction was carried out in 30-mL vials sealed with a septum. The initiator was dissolved in a 0.037 M PhCl stock solution. The RIM monomer was added to this initiator stock solution. After mixing the RIM monomer with the initiator stock solution at room temperature, the mixture was heated in an aluminum heating block without stirring. b The start time is defined as the moment when the reaction mixture begins to lose fluidity and the temperature rises sharply, as observed by the vaporization and condensation of residual volatiles in the bottle (the two usually occur rapidly in succession). c The determination was made by thermogravimetric analysis of the polymer. d Glass transition temperature.

[0149] (The above compound 3 is the same as compound 2 disclosed in Heppekausen and Fürstner as mentioned in the background section.) Example 6 Table 4 shows the ring-opening metathesis polymerization of "ultra-pure" 1,5-cis,cis-cyclooctadiene (COD) without a Lewis acid activator, initiated by compound 2 (compound 2 is identical to compound 3 disclosed in Heppekausen and Fürstner as mentioned in the Background section). Compound 2 is as follows:

[0150] Table 4

[0151] Overview: "Ultrapure" COD was thoroughly purified by reflux over calcium hydride under an argon atmosphere for 24 hours prior to distillation. The distilled COD was further dried with activated 3A molecular sieves for at least 24 hours before filtration and storage. The reaction was carried out in 4-mL vials sealed with a septum. The solution was delivered in a 0.037 M PhCl stock solution in the vial, and the substrate was added thereto. No additional solvent was used in any reaction. The vials were heated at 70°C for the given reaction time in an aluminum heating block. 1 H NMR analysis was used to determine the conversion rate.

[0152] Example 7 This embodiment illustrates Mo(NAr) diiPr Additional experimental evidence for the thermal activation of )(CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 1. Van Toff analysis Based on Fürstner's findings and claims (such as doi.org / 10.1002 / anie.201102012 and WO 2012 / 116695 mentioned in the background section), based on them 1 ¹H NMR spectroscopy also revealed Mo(NAr) as shown in the following scheme. diiPr (CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 and Mo(NAr) diiPr The complex )(CHCMe2Ph)(OC(CF3)2Me)2(1,10-phenanthroline)3 is non-dissociative at room temperature (298 K), which prevented us from determining the thermodynamic stability (stability constant) of these complexes. However, we demonstrated that the bipyridine adduct 2 dissociates even at moderately elevated temperatures. This finding allowed us to experimentally determine the equilibrium constant of 2 at high temperatures (>30 °C) and subsequently estimate its stability constant at room temperature.

[0153]

[0154] Solution: Schrock catalyst Mo(NAr) diiPr (CHCMe2Ph)(OC(CF3)2Me)21 and its significant 18-electron adducts (the above compound 2 is the same as compound 3 in Fürstner's scheme as mentioned in the background section; the above compound 3 is the same as compound 2 in Fürstner's scheme as mentioned in the background section).

[0155] Mo(NAr) was measured in the temperature range of 306.60 K to 372.95 K. diiPr The equilibrium constant of (CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 as a function of temperature increases by approximately 11 K between experiments (entries 2 to 8 in Table 5). This is based on the degree of dissociation of adduct 2, i.e., based on... 1 The 2- and correspondingly released 14-electron complex Mo(NAr) in the 1H NMR sample (0.0101 M, toluene-d8) diiPr The mole fraction of )(CHCMe2Ph)(OC(CF3)2Me)21 was used to determine the equilibrium constant (or stability constant) at each temperature. The measured lnK values ​​were plotted against the corresponding 1 / T values. Figure 5 These two datasets show the expected linear relationship according to the linear form of the van Toff equation (linear form: K - Equilibrium constant, DH r -Standard enthalpy of reaction, DS r-Standard reaction entropy). The slope of the line is positive, indicating that the net enthalpy change of coordination of 2,2'-bipyridine with 1 is negative, and the formation of 2 is an exothermic reaction.

[0156] use Figure 5 The linear relationship shown is used by extrapolation to determine the stability constant at 25 degrees Celsius / 298 K: K 甲苯-d8，298K =984609 M -1 (Table 5, Item 1). This value is significantly higher than the upper limit of the range for defining the stability constant of the room-temperature dissociated (“self-activated”) 18-electron adduct of Schrock catalysts, as described in GB 2 537 416, WO2021 / 239891, and doi.org / 10.1038 / s42004-021-00503-4. However, note that the stability constant of 2 decreases significantly with increasing temperature, reaching 161 M at 372.9 K. -1 (Item 8 in Table 5), which means in 1 Under the conditions of H NMR experiments (0.0101 M, toluene-d8, 272.9 K), 2 dissociates >50% into catalytically active 1 and 2,2'-bipyridine.

[0157] Table 5 below shows the results for Mo(NAr) diiPr The stability constant of (CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 as a function of temperature is based on the 2- and corresponding 14-electron complex Mo(NAr) diiPr The molar ratio of )(CHCMe2Ph)(OC(CF3)2Me)21, through 1 The determination was performed by ¹H NMR experiment (0.0101 M, toluene-d8 solution). At 298.15 K, dissociation was negligible, and the corresponding stability constant was determined by extrapolation.

[0158]

[0159] 1. Use "thermally activated" Mo(NAr) diiPr (CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 and "self-activated" Mo(NAr) diiPr (CHCMe2Ph)(OC(CF3)2Me)2(4,4-dibromo-2,2'-bipyridine)4 self-cross-metathesis of 9-DAME The self-cross metathesis of methyl 9-decenoate (9-DAME) was chosen as the model reaction to demonstrate the "thermally activated" Mo(NAr) diiPr(CHCMe2Ph)(OC(CF3)2Me)2(2,2'-bipyridine)2 and "self-activated" Mo(NAr) diiPr The significantly different catalytic behavior of (CHCMe2Ph)(OC(CF3)2Me)2(4,4-dibromo-2,2'-bipyridine)4. Note that 2 is non-dissociative at room temperature, and Fürstner describes it as inactive in the absence of a Lewis acid. Fürstner claims that a Lewis acid must be added to 2 to isolate the 2,2'-bipyridine ligand from the adduct, thereby releasing the active Mo(NAr)4. diiPr )(CHCMe2Ph)(OC(CF3)2Me)21. Mo(NAr diiPr (CHCMe2Ph)(OC(CF3)2Me)2(4,4-dibromo-2,2'-bipyridine)4 was developed by XiMo and structurally tuned to dissociate at room temperature, enabling the release of active Mo(NAr) in the absence of Lewis acids. diiPr (CHCMe2Ph)(OC(CF3)2Me)21, and thus capable of catalyzing olefin metathesis reactions without the addition of Lewis acids. Based on the well-described non-dissociative properties of 2, the adduct did not provide any significant 9-DAME conversion after 2 hours of reaction at 21 °C (entry 1 in Table 6), and the conversion remained negligible during the 24-hour observation period (7% conversion after 24 hours, entry 3 in Table 6). Under the same conditions, the room-temperature dissociated (“self-activated”) 4 provided 28% conversion after 2 hours and 72% conversion after 24 hours (entries 2 and 4 in Table 6), demonstrating a significant difference between the two adducts despite their similar structures and proving the earlier-developed “self-activation” concept.

[0160] Even more importantly, the reaction at 70°C perfectly demonstrates the "thermal activation" concept claimed in the current application. At the elevated temperature, 2 also dissociates, thus becoming catalytically active, and provides performance very similar to the "self-activated" 4. After 1 hour of reaction time, the yield of the self-cross-metathesis product was 89% in the case of 2 and 98% in the case of 4, while after 2 hours the yield was 96% in the case of 2 and 99% in the case of 4 (Entries 5, 6 and 8, 9 of Table 6). The similar E:Z ratio indicates the fact that both precatalysts release the same active substance 1. It is also noteworthy that both adducts outperform the catalytically active parent complex 1, thus demonstrating the chemoprotective effect of the N-heterocyclic Lewis bases 2,2'-bipyridine and 4,4'-dibromo-2,2'-bipyridine (Entries 7, 10 of Table 6 versus entries 5, 6, 8, 9). Table 6: Self-cross metathesis of methyl 9-decenoate (9-DAME) , I

[0161] Conditions: 9-DAME: 500 mg / 560 μL, 300 mol ppm of catalyst added from 0.0035 M benzene stock solution, vial opened for ethylene release; reaction mixture stirred at given temperature for given reaction time; and sample taken from reaction mixture analyzed by GC.

Claims

1. A composition capable of undergoing a metathesis reaction, said composition comprising: (X) An 18-electron alkylene compound, wherein the 18-electron alkylene compound is formed by complexing a 14-electron Schrock alkylene compound with a bidentate ligand selected from: (a) Optionally substituted 1,10-phenanthroline; and (b) Optional substituted 2,2'-bipyridine; as well as (Y) One or more compounds, each containing an alkene double bond; in, The composition satisfies the following conditions: (c) Does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate or zinc trifluoroacetate; (d) At temperatures above 50°C; Preferably, the composition satisfies the following conditions: (e) It does not contain an inert solvent for the compound (X) and / or the compound (Y).

2. The composition according to claim 1, wherein, The composition comprises: Compounds of formula (X1), ， I in, M is Mo or W; A is selected from NR 1 Or O, where R 1 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl; B is selected from pyrrole, indole, and pyrazole, which are substituted respectively; and C is selected from OR 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B and C are the same, where C is selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B differs from C, where both B and C are selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; D is 1,10-phenanthroline or substituted 1,10-phenanthroline; R 3 and R 4 H and C independently 1-10 Alkyl or aryl, optionally substituted C 1-10 Alkyl and aryl; and wherein, R 3 and R 4 Only one of them is hydrogen; or The composition comprises: Compounds of formula (X2) II ， II in, M is Mo or W; A is selected from NR 1 Or O, where R 1 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl; B is selected from pyrrole, indole, and pyrazole, which are substituted respectively; and C is selected from OR 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B and C are the same, where C is selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; or B differs from C, where both B and C are selected from OR. 2 , where R 2 The C that is arbitrarily replaced is chosen separately. 1-10 Alkyl or aryl or (C 1-10 alkyl)3Si or (aryl)3Si; D is 2,2'-bipyridine or substituted 2,2'-bipyridine; R 3 and R 4 H and C independently 1-10 Alkyl or aryl, optionally substituted C 1-10 Alkyl and aryl; and wherein, R 3 and R 4 Only one of them is hydrogen.

3. The composition according to claim 2, wherein, R 1 They are independently controlled by C 1-10 Alkyl, C 1-10 One or more substituted C atoms from alkoxy, phenyl, halogen, CN, and CF3 1-10 Alkyl or phenyl.

4. The composition according to any one of claims 2 to 3, wherein, B is selected from those independently of C. 1-10 Alkyl, C 1-10 One or more substituted pyrroles, indoles, and pyrazoles of alkoxy or phenyl groups.

5. The composition according to any one of claims 2 to 4, wherein, R 2 Selected from the C that is arbitrarily replaced 1-10 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-dissociable in the composition at at least at room temperature.

7. The composition according to any one of claims 2 to 6, wherein, 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 the same as C, where C is an electron-withdrawing group and 1,10-phenanthroline is unsubstituted; or B is the same as C, wherein C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more electron-donating groups; or B differs from C in that both B and C are 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 by one or more electron-donating groups; or B is the same as C, where C is an electron-withdrawing group and 2,2'-bipyridine is unsubstituted; or B is the same as C, wherein C is an electron-withdrawing group, and 2,2'-bipyridine is substituted by one or more electron-donating groups; or B differs from C in that both B and C are electron-withdrawing groups, and 2,2'-bipyridine is unsubstituted; or B differs from C, where both B and C are electron-withdrawing groups, and 2,2'-bipyridine is substituted by one or more electron-donating groups; Preferably, wherein, B is selected from pyrrole, indole, and pyrazole, which are substituted respectively, and C is selected from OR 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 1-10 Alkyl or aryl or (C 1-10 (alkyl)3Si or (aryl)3Si; and 1,10-phenanthroline is unsubstituted or selected from C 1-5 Alkyl, C 1-5 Alkyl group, -O-(CH2) n One or more substituted 1,10-phenanthrolines of -O- and phenyl groups, n=1 or 2; or B and C are the same, where C is selected from OR. 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 1-10 Alkyl or aryl or (C 1-10 (alkyl)3Si or (aryl)3Si; and 1,10-phenanthroline is unsubstituted, or 1,10-phenanthroline is selected from C 1-5 Alkyl, C 1-5 Alkyl group, -O-(CH2) n One or more substitutions in -O- and phenyl, n=1 or 2; or B and C are the same, where C is selected from OR. 2 , where R 2 C is a carbon that is substituted by one or more of halogens or CF3. 1-10 Alkyl or aryl or (C 1-10 (alkyl)3Si or (aryl)3Si; and 2,2'-bipyridine is unsubstituted or selected from C 1-5 Alkyl, C 1-5 One or more substitutions of alkoxy or phenyl.

8. The composition according to any one of claims 6 or 7, wherein, The compound is non-dissociable at temperatures up to 50°C.

9. The composition according to any one of claims 2 to 8, wherein, R 3 and R 4 H and C independently 1-10 alkyl or aryl, wherein C 1-10 The alkyl or aryl group is independently substituted by one or more of the following groups: C 1-5 Alkyl groups, C substituted with one or more halogens 1-5 Alkyl, C 1-5 Alkoxy, phenyl, halogen; or In the compositions at temperatures of 50°C or below, compared to compositions at temperatures above 50°C, the molar ratio of compound (Y), comprising one or more compounds each containing an olefinic double bond, to compound (X), compound I (X1), or compound II (X2) is greater than 2000, 4000, 6000, 8000, 10000, 20000, 30000, or 40000; or Wherein, the temperature is higher than 55℃, or higher than 60℃, or higher than 70℃, or higher than 80℃, or higher than 90℃, or higher than 100℃; or The temperature is in the range of 50°C to 140°C, 55°C to 130°C, or 60°C to 120°C.

10. The composition according to any one of claims 1 to 9, wherein, The compound (X) is selected from one of the following compounds 5 to 8: ， Among them, R 24 =Methyl, phenyl; R 25 R 26 =H, methyl, CF3; Z = methyl, isopropyl, halogen; or The compound (X) is selected from one of the following compounds III to VI: ;or The compound (X) is selected from one of the following compounds: ， R = Me, Ph; Ar = 2,6-diisopropylphenyl; ;or The compound (X) is selected from: ,and .

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

12. The composition according to any one of claims 1 to 11, wherein, The stability constant is greater than 300,000 L*mol. -1 or greater than 350,000 L*mol -1 or greater than 400,000 L*mol -1 .

13. A method for preparing a composition as defined in any one of claims 1 to 12, the method comprising: Provide compound (X) and compound (Y); Heat the mixture of the provided compounds to a temperature above 50°C; in, The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; Preferably, the composition does not contain an inert solvent for the compound (X) and / or the compound (Y).

14. A method for activating a compound (X) as defined in any one of claims 1 to 12, for initiating an olefin metathesis reaction in a composition comprising one or more compounds (Y), each comprising an olefinic double bond, said method comprising: The composition comprising compound (X) and compound (Y) is heated to a temperature above 50°C; in, The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; Preferably, the composition does not contain an inert solvent for the compound (X) and / or the compound (Y); or A method for performing a metathesis reaction, the method comprising: The composition comprising compound (X) as defined in any one of claims 1 to 10 and one or more compounds (Y) is heated to a temperature above 50°C. in, The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; Preferably, the composition does not contain an inert solvent for the compound (X) and / or the compound (Y).

15. A composition comprising: The compound (X) and one or more compounds (Y) as defined in any one of claims 1 to 12; in, The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; The temperature of the composition is below 50°C; Preferably, the composition does not contain an inert solvent for the compound (X) and / or the compound (Y).

16. Use of the composition as defined in claim 15 in a metathesis reaction, said use comprising: The composition is heated to a temperature above 50°C.

17. Use of compound (X) to initiate a metathesis reaction in a composition comprising one or more compounds (Y) as defined in any one of claims 1 to 12, said use comprising: The composition comprising compound (X) and compound (Y) is heated to a temperature above 50°C; in, The composition does not contain one or more Lewis acids selected from MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, zinc trifluoromethanesulfonate, or zinc trifluoroacetate; Preferably, the composition does not contain an inert solvent for the compound (X) and / or the compound (Y).

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