Air-stable imido alkylidene complexes and their use in olefin metathesis reactions.

Abstract

The present invention relates to Schrock-alkylidene complexes containing phenanthroline ligands that dissociate upon exposure to solvent, releasing catalytically active complexes in olefin metathesis reactions without the need for a Lewis acid, such as zinc chloride, to remove the ligand. Thus, the phenanthroline complexes are self-activating.

Description

[Technical Field]

[0001] The present invention relates to an 18-electron molybdenum or tungsten alkylidene complex formed from a 14-electron molybdenum or tungsten alkylidene complex and 1,10-phenanthroline as a neutral bidentate ligand. The invention also relates to a method for preparing an 18-electron catalyst, a system containing the 18-electron complex and the 14-electron complex, a method for preparing a 14-electron complex from the 18-electron complex, and a method for performing olefin metathesis reactions using the complex. [Background technology]

[0002] Olefin metathesis reactions catalyzed by transition metal catalysts, such as molybdenum or tungsten alkylidene catalysts—also known as Schrock catalysts—are among the most important reactions in synthetic organic chemistry. A valuable class of known catalysts is the group of metal imido alkylidene complexes. The effectiveness of these catalysts 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 often limits their usefulness.

[0003] To improve air stability, WO 2012 / 116695 proposes stabilizing such catalysts by complexing them with bidentate heterocycles such as 2,2'-bipryridine and 1,10-phenanthroline. Exemplary 1,10-phenanthroline complexes are complexes 5 to 8. [ka] R 24 = methyl, phenyl; R 25 , R 26 =H, methyl, CF3; Z=methyl, isopropyl, halogen.

[0004] However, such air-stable products are not catalytically active, and the active form of the catalyst must be released by exposure to a Lewis acid, such as MgCl, MgBr, MgI, MnCl, MnBr, MnI, FeCl, AlCl, CuCl, ZnCl, ZnBr, ZnI, Zn(CFSO), or Zn(CFCOO), and optionally, heat. The presence of the Lewis acid and the formation of an adduct of the phenanthroline with the Lewis acid can adversely affect the metathesis reaction and generally results in a complex workup of the reaction mixture to isolate the reaction products.

[0005] EP 3 268 377 B1 discloses tungsten imido alkylidene catalysts stabilized with 1,10-phenanthroline. The catalyst must be activated by the addition of a Lewis acid such as zinc chloride. Exemplary complexes are complexes III to VI. [ka]

[0006] GB 2 537 416 discloses metathesis catalysts complexed with 2,2'-bipyridine that can be activated by dissolving in a solvent without the need for the addition of a Lewis acid. The authors of GB 2 537 416 demonstrate that these bipyridine adducts are unstable, and refer to the spontaneous release of the active catalyst as "self-activated catalyst." They conclude that this is a property of a relatively small number of compounds.

[0007] The concept of unstable bipyridine adducts has also been published in the scientific literature (Gulyas, H. et al., "Air-stable 18-electron adducts of Schrock catalysts with tuned stability constants for spontaneous release of active species," Commun. Chem. 4, 71 (2021); https: / doi.org / 10.1038 / s42004-021-00503-4). Summary of the Invention

[0008] Object of the invention There is a continuing need in the industry to provide alkylidene complexes of molybdenum and tungsten suitable for catalyzing olefin metathesis reactions, which complexes have improved air stability, and which do not require chemical activation.

[0009] Summary of the Invention This object is achieved with an 18-electron complex of formula I according to independent claim 1. Further independent claims define a method for preparing a complex of formula I, a system comprising an equilibrium between a complex of formula I and a 14-electron complex of formula II, a method for preparing a 14-electron complex of formula II from an 18-electron complex of formula I, and a method for carrying out an olefin metathesis reaction using a complex of formula I. Preferred embodiments are specified in the respective dependent claims.

[0010] Without being bound by theory, the inventors believe that depending on the substitution pattern of the complex of formula I, particularly with respect to at least D (1,10-phenanthroline and substituted 1,10-phenanthroline) or C (alkoxides, aryloxides) or D and C, the stability constant K of the complex of formula I with respect to the neutral bidentate ligand in the solvent is greater than 5L when measured at 298K when the complex of formula I is dissolved in the solvent. * mol -1 ~250,000L * mol -1 We found that the finite stability constant K can be tuned to the range of 0.01 to 0.01. Therefore, this finite stability constant K contributes to the equilibrium in the selected solvent between the 18-electron complex containing the bidentate ligand, which is inactive in olefin metathesis reactions, and the 14-electron complex released by dissociation of the bidentate ligand, which is catalytically active in olefin metathesis reactions.

[0011] Conversely, complexes with a virtually infinite stability constant K, i.e., a stability constant that is too high in a given solvent, are too stable for the active form to be released from them, which is the case for complexes that require the aid of a Lewis acid to remove the bidentate ligand, as known from the prior art, as mentioned in the Background section.

[0012] Complexes with stability constants that are too low, i.e., approach zero in a given solvent, will not form 18-electron complexes with neutral bidentate ligands.

[0013] In a research program, the inventors of the present invention have measured at 298 K when the complex of formula I is dissolved in a solvent of 5 L. * mol -1 ~250,000L * mol -1 It has been found that Schrock-alkylidene complexes of formula I, having stability constants in the range of , are air-stable and catalytically active in olefin metathesis reactions without the need for removal of the bidentate ligand by a Lewis acid and thus without the unnecessary formation of the corresponding by-product, i.e., such complexes are self-activated. This is a significant improvement in view of the cited prior art discussed in the Background section.

[0014] It is worth noting that the inventors' discovery in GB 2 537 416 A that Schrock-alkylidene complexes having 2,2'-bipyridine as a neutral ligand can be activated by dissolution in a solvent without the addition of a Lewis acid, a property that is characteristic of a relatively small number of selected compounds, can be explained. Without being bound by theory, the inventors speculate that the lower complexing ability of 2,2'-bipyridine compared to 1,10-phenanthroline ligands is due to the conformational flexibility of bipyridine and the fact that the thermodynamically most stable conformer of bipyridine has a torsion angle of about 40° around the pyridine ring, which is not optimal for bidentate complex formation. This is also confirmed in the above-mentioned Gulyas publication.

[0015] Conversely, the rigid backbone of 1,10-phenanthroline is ideal for bidentate complex formation.

[0016] The present invention relates to the following items. [Item 1] A complex of formula I, [ka] M=Mo or W; A is NR 1 or O, and R 1 But C 1~10 alkyl or aryl, each optionally substituted; B is selected from pyrrole and pyrazole, each optionally substituted; or B is C, C is OR 2 Selected from R 2 But C 1~10 alkyl or aryl, each optionally substituted; D is a neutral bidentate ligand, said ligand being 1,10-phenanthroline or a substituted 1,10-phenanthroline; R 3 and R 4 However, independently, H, C 1~10 alkyl or aryl, C 1~10 The alkyl and aryl are each optionally substituted, and R 3 and R 4 Only one of the is hydrogen, Complex. [Item 2] The complex of formula I is characterized by a stability constant K with respect to the neutral ligand in the solvent, and the substitution pattern of the complex of formula I with respect to at least one of D or C or D and C is such that when the complex of formula I is dissolved in the solvent, the stability constant K is greater than or equal to 5L when measured at 298K. * mol -1 ~250,000L * mol -1and preferably the substitution pattern of at least one of D or D and C is selected so as to adjust the stability constant K to within the range of 5L when measured at 298 K when the complex of formula I is dissolved in a solvent. * mol -1 ~250,000L * mol -1 The complex according to item 1, wherein the complex is selected so as to adjust the range of [Item 3] R 1 However, each independently, C 1~10 Alkyl, C 1~10 C substituted with one or more of alkoxy, phenyl, halogen, CN, and CF 1~10 3. The complex according to item 1 or 2, wherein the alkyl or phenyl group is alkyl or phenyl. [Item 4] B, independently, C 1~10 Alkyl, C 1~10 4. The complex according to any one of items 1 to 3, which is a pyrrole and pyrazole substituted with one or more of alkoxy or phenyl. [Item 5] R 2 C independently substituted with one or more of halogen or phenyl 1~10 alkyl; or substituted phenyl, independently selected from the group consisting of C 1~10 Alkyl, C substituted with one or more halogens 1~10 Alkyl, C 1~10 phenyl substituted with one or more of alkoxy, phenyl, halogen, —(CH)— which forms a cyclic ring together with the phenyl, or —(CH═CH-CH═CH)— which forms a cyclic ring together with the phenyl, or phenyl substituted with —O-silyl; 5. The complex according to any one of items 1 to 4. [Item 6] The phenanthroline may independently contain one or more electron donating substituents, preferably C 1~10 Alkyl, C 1~10 substituted with one or more electron-donating substituents selected from alkoxy, phenyl, or substituted with one or more electron-withdrawing substituents, preferably one or more electron-withdrawing substituents selected from halogen, CN, CF3 and CCl3; 6. The complex according to any one of items 1 to 5. [Item 7] R 3 and R 4 However, independently H, C 1~10 alkyl or aryl, C 1~10 alkyl or aryl, independently C 1~5 Alkyl, C substituted with one or more halogens 1~5 Alkyl, C 1~5 7. The complex according to any one of items 1 to 6, which is substituted with one or more of alkoxy, phenyl, and halogen. [Item 8] K is 10L * mol -1 ~150,000L * mol -1 or 10L * mol -1 ~100,000L * mol -1 or 10L * mol -1 ~50,000L * mol -1 or 10L * mol -1 ~10,000L * mol -1 or 10L * mol -1 ~5000L * mol -1 or 10L * mol -1 ~500L * mol -1 8. The complex according to any one of items 2 to 7, wherein [Item 9] 9. The complex according to any one of items 2 to 8, wherein the concentration of the complex in the solvent is in the range of 0.0001 to 0.5 M. [Item 10] 10. The complex according to any one of items 2 to 9, wherein 1,10-phenanthroline and substituted 1,10-phenanthroline are selected to adjust K. [Item 11] 11. The complex according to any one of items 2 to 10, wherein the 1,10-phenanthroline is substituted with one or more electron-donating groups to increase K compared to a complex of formula I having the same substitution pattern for A, B, and C, but in which the bidentate ligand D is unsubstituted 1,10-phenanthroline. [Item 12] 11. The complex according to any one of items 2 to 10, having the same substitution pattern for A, B, and C, but wherein the 1,10-phenanthroline is substituted with one or more electron-withdrawing groups to decrease K compared to a complex of formula I having the same substitution pattern for A, B, and C, but wherein the bidentate ligand D is unsubstituted 1,10-phenanthroline. [Item 13] 13. The complex according to any one of items 2 to 12, wherein C is selected to coordinate K, and C is an alkoxide, and C is characterized in terms of its alkoxide cone angle, the alkoxide cone angle and its determination being as defined herein. [Item 14] 14. The complex according to item 13, wherein the alkoxide cone angle is increased to decrease K compared to a complex having the same substitution pattern for A, B, and D; or wherein the alkoxide cone angle is decreased to increase K compared to a complex having the same substitution pattern for A, B, and D. [Item 15] 13. The complex according to any one of items 2 to 12, wherein C is selected to coordinate K and C is an aryloxide, and C is characterized in terms of its steric bulk. [Item 16] 16. A complex according to item 15, wherein the steric bulk is increased to decrease K compared to a complex having the same substitution pattern for A, B and D; or wherein the steric bulk is decreased to increase K compared to a complex having the same substitution pattern for A, B and D. [Item 17] The complex has the formula: [ka] R is C(CH3)3, C(CH3)2C6H5, C6H5, or o-(C 1~4 )-alkoxyC6H4, Preferably, R is o-(C 1~4 )-alkoxyC6H4, More preferably, the complex is [ka] [O-TBS=O-Si(t-butyl)(Me)2] 17. The complex according to any one of items 1 to 16. [Item 18] A method for producing a complex, comprising the steps of: [ka] A, B, C, R 3 and R 4 wherein R has the meaning given for the complex of formula I, in a solvent, to 1,10-phenanthroline or a substituted 1,10-phenanthroline. [Item 19] 19. The method of claim 18, further comprising isolating the complex of formula I in solid form. [Item 20] 20. The method according to item 18 or 19, wherein the complex of formula I is isolated by filtration. [Item 21] 20. The method according to item 18 or 19, wherein the complex of formula I is isolated by evaporating the solvent. [Item 22] A complex of formula I according to any one of items 1 to 17, a complex of formula II according to item 18, A system comprising: A system in which a complex of formula I and a complex of formula II are dissolved in a solvent. [Item 23] 23. The system of claim 22, wherein the system does not contain a Lewis acid. [Item 24] 24. The system according to item 23, wherein the Lewis acid is MgCl, MgBr, MgI, MnCl, MnBr, MnI, FeCl, AlCl, CuCl, ZnCl, ZnBr, ZnI, Zn(CFSO) or Zn(CFCOO). [Item 25] dissolving a complex of formula I according to any one of items 1 to 17 in a solvent; Item 19. A method for preparing a complex of formula II according to item 18, comprising: [Item 26] 26. The method of claim 25, wherein the method is carried out in the absence of a Lewis acid. [Item 27] 27. The method of claim 26, wherein the Lewis acid is MgCl, MgBr, MgI, MnCl, MnBr, MnI, FeCl, AlCl, CuCl, ZnCl, ZnBr, ZnI, Zn(CFSO), or Zn(CFCOO). [Item 28] 1. A method for conducting a metathesis reaction of a compound containing an olefinic double bond, comprising: adding the complex according to any one of items 1 to 17 to an olefinic compound in the presence of a solvent; A method comprising: [Item 29] 29. The method according to item 28, wherein the compound containing an olefinic double bond is a solvent. [Item 30] 30. The method of claim 28 or 29, wherein the metathesis reaction is carried out in the absence of a Lewis acid. [Item 31] 31. The method of claim 30, wherein the Lewis acid is MgCl, MgBr, MgI, MnCl, MnBr, MnI, FeCl, AlCl, CuCl, ZnCl, ZnBr, ZnI, Zn(CFSO), or Zn(CFCOO). [Brief explanation of the drawings]

[0017] [Figure 1]Schematic diagram of an alkoxide with an O-C tertiary bond and an O-A line segment, where A is the outermost atom of the group bonded to the C tertiary. This diagram can be used to calculate the alkoxide cone angle. [Figure 2] 1H NMR spectrum of complex A1 in C6D6 (c=0.01 M) at 298 K. [Figure 3] 1H NMR spectrum of complex A2 in C6D6 (c=0.01 M) at 298 K. [Figure 4] 1H NMR spectrum of complex A3 in C6D6 (c=0.01 M) at 298 K. DETAILED DESCRIPTION OF THE INVENTION

[0018] According to a first aspect, the present invention relates to a complex of formula I, [ka] M=Mo or W; A is NR 1 or O, and R 1 is C 1~10 alkyl or aryl, each optionally substituted; B is selected from pyrrole and pyrazole, each optionally substituted; or B is C; C is for OR 2 Selected from R 2 is alkyl, preferably C 1~10 alkyl, or aryl, each optionally substituted; R 3 and R 4 are independently H, C 1~10 alkyl or aryl, C 1~10 The alkyl and aryl are optionally substituted, and R 3 and R 4 Only one of the is hydrogen, D is a neutral bidentate ligand, said ligand being 1,10-phenanthroline or a substituted 1,10-phenanthroline, and preferably the complex of formula I is characterized by a stability constant K for the neutral ligand in a solvent, and the substitution pattern for at least one of D or C and D of the complex of formula I is such that when the complex of formula I is dissolved in the solvent, the stability constant K is 5L when measured at 298K. * mol -1 ~250,000L * mol -1 The adjustment is selected to be in the range of

[0019] According to the present invention, M is Mo or W.

[0020] In one embodiment, M is W.

[0021] According to the present invention, A is NR 1 or O, and R 1 is alkyl, preferably C 1~10 alkyl, or aryl, each optionally substituted.

[0022] In a preferred embodiment, A is NR 1 and R 1 is C 1~10 It is alkyl or aryl, each optionally substituted.

[0023] As used herein, for example, R 1 The term "alkyl or C" used in the definition 1~10 "Alkyl" includes straight-chain, branched, cyclic and alicyclic alkyl. 1~10 Alkyl is C 1~5 In another embodiment, C 4~10 Alkyl is preferred.

[0024] In one embodiment, R 1 is t-butyl or 1-adamantyl.

[0025] As used herein, for example, R1 The term "aryl" as used in the definition of includes phenyl, naphthyl, anthracenyl, and phenanthryl, each of which is optionally substituted.

[0026] Suitable substituents are C 1~10 Alkyl, C 1~10 It may be selected from one or more of alkoxy, phenyl, halogen, CN, and CF3.

[0027] The aryl is preferably phenyl.

[0028] In one embodiment, R 1 is C 1~10 Alkyl, C 1~10 C independently substituted with one or more of alkoxy, phenyl, halogen, CN, and CF 1~10 It is alkyl or phenyl.

[0029] According to the present invention, B is selected from pyrrole and pyrazole, each optionally substituted; or B is C.

[0030] In one embodiment, each B is independently selected from the group consisting of C 1~5 Alkyl, C 1~5 Pyrroles and pyrazoles substituted with one or more of alkoxy or phenyl.

[0031] According to the present invention, C is OR 2 Selected from R 2 are each optionally substituted C 1~10 It is alkyl or aryl.

[0032] In one embodiment, R 2 is independently a C substituted with one or more of halogen or phenyl; 1~5 alkyl; or substituted phenyl, independently selected from the group consisting of C 1~5 Alkyl, C substituted with one or more halogens 1~5 Alkyl, C 1~5It is phenyl substituted with one or more of alkoxy, phenyl, halogen, —(CH2)4— which forms a cyclic ring together with the phenyl, or —(CH═CH-CH═CH)— which forms a cyclic ring together with the phenyl, or phenyl substituted with —O-silyl.

[0033] The term "silyl" may refer to a silyl group that forms a covalent bond between silicon and oxygen.

[0034] Suitable silyl groups are, for example, t-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and triphenylsilyl.

[0035] According to the present invention, D is a neutral bidentate ligand, said neutral ligand being 1,10-phenanthroline or a substituted 1,10-phenanthroline, both N atoms of the phenanthroline skeleton being bonded to M, thus forming a bidentate ligand.

[0036] In one embodiment, the phenanthroline is substituted with one or more electron donating groups.

[0037] In one embodiment, the 1,10-phenanthroline is independently selected from the group consisting of C 1~5 Alkyl, C 1~5 Alkoxy, -O-(CH2) n -O- (n=1 or 2), and phenyl, which groups represent electron-donating groups in the sense of the present invention.

[0038] In other embodiments, the 1,10-phenanthroline is substituted with one or more electron-withdrawing groups.

[0039] In one embodiment, the 1,10-phenanthroline is independently substituted with halogen, cyano, CF or CCl, which groups represent electron-withdrawing groups in the sense of the present invention.

[0040] Commercially available phenanthrolines include, for example: [ka] [ka]

[0041] According to the present invention, R 3 and R 4 are independently H, C 1~10 alkyl or aryl, where alkyl and aryl are optionally substituted; R 3 and R 4 Only one of them is hydrogen.

[0042] In one embodiment, R 3 and R 4 are independently H, C 1~10 alkyl or aryl, C 1~10 Alkyl or aryl are independently C 1~5 Alkyl; halogen, C 1~5 C substituted with one or more of alkoxy, phenyl, and halogen 1~5 alkyl, substituted with one or more of:

[0043] According to the present invention, the complex of formula I is characterized by a stability constant K for the neutral ligand in the solvent, K being 5L at 298 K. * mol -1 ~250,000L * mol -1 (5M -1 ~250,000M -1 ) range.

[0044] The term "stability constant" is used synonymously with the term "association constant." It is the reciprocal of the dissociation constant. Terms such as "binding constant" and "formation constant" are also sometimes used synonymously with the term "stability constant."

[0045] K can be determined according to known methods employing the law of mass action.

[0046] Suitable solvents are preferably organic aromatic solvents such as benzene, toluene, xylene or chlorobenzene, chlorinated hydrocarbons such as dichloromethane or trichloromethane, or the substrate to be metathesized.

[0047] According to the present invention, the substitution pattern for at least D or C and D of the complex of formula I is such that when the complex of formula I is dissolved in the solvent, the stability constant K for a neutral bidentate ligand in the solvent is 5L when measured at 298 K. * mol -1 ~250,000L * mol -1 The adjustment is selected to be in the range of

[0048] According to the present invention, K is the solubility of the complex of formula I in a solvent when measured at 289 K. * mol -1 ~250,000L * mol -1 The range is.

[0049] In one embodiment, K is 10L * mol -1 ~150,000L * mol -1 or 10L * mol -1 ~100,000L * mol -1 or 10L * mol -1 ~50,000L * mol -1 or 10L * mol -1 ~10,000L * mol -1 or 10L * mol -1 ~5,000L * mol -1 or 10L * mol -1 ~500L * mol -1is adjusted to the range.

[0050] In one embodiment, the concentration of the complex in the solvent is in the range of 0.0001 to 0.5 M (0.0001 to 0.5 mol / L).

[0051] In one embodiment, 1,10-phenanthroline and substituted 1,10-phenanthrolines are selected to adjust K.

[0052] In one embodiment, the 1,10-phenanthroline has the same substitution pattern for A, B, and C, but is substituted with one or more electron-donating groups to increase K compared to a complex of Formula I in which the bidentate ligand D is unsubstituted 1,10-phenanthroline.

[0053] In another embodiment, the 1,10-phenanthroline is substituted with one or more electron-withdrawing groups to decrease K compared to a complex of Formula I having the same substitution pattern for A, B, and C, but where the bidentate ligand D is unsubstituted 1,10-phenanthroline.

[0054] In other embodiments, C is selected to adjust K, provided that C is an alkoxide, and C is characterized in terms of its alkoxide cone angle.

[0055] The cone angle is defined by C.A. Tolman in J. Am. Chem. Soc., 1970, 92, 2956-2965 and Chem. Rev., 77, 313 (1977) with the metal as the apex.

[0056] The cone angle used in this disclosure for C is defined such that the oxygen in C that connects the alkyl moiety to M is at its vertex, as shown in Figure 1. This cone angle α is determined according to steps 1 to 4 below.

[0057] 1. Find the most stable identity of the alkoxide ligand in the desired complex.

[0058] 2. Determine the β angle from the structure. The β angle is the angle 第3級 Bond and OA line segment (A is C 第3級 A is the angle between the outermost atoms of the group bonded to C. 第3級 The outermost atom of the group bonded to the O, C 第3級 and consider the center of the A atom).

[0059] 3. Calculate the γ angle from the OA distance and r, the van der Waals radius of A. Sinγ=r / A.

[0060] 4. When the three organic ligands in the alkoxide are the same, the alkoxide is C 3v Because of the symmetry, the normal cone will cover the ligand, so α = 2(β + γ).

[0061] In the case of three different ligands, the steric parameters are determined by the C 3v It is defined as the average of the symmetric alkoxide cone angles. Technically, it is the average of the three β+γ half angles, multiplied by 2, as follows:

number

[0062] The cone angle is used as a measure for the bulkiness of the alkoxide ligand.

[0063] In one embodiment, an increase in the alkoxide cone angle typically results in a decrease in K compared to a complex having the same substitution pattern for A, B, and D.

[0064] In other embodiments, a decrease in the alkoxide cone angle typically results in an increase in K compared to a complex having the same substitution pattern for A, B, and D.

[0065] Thus, in a preferred embodiment, K can be adjusted with respect to its cone angle by C, provided that C is an alkoxide.

[0066] In a preferred embodiment, the alkoxide cone angle is in the range of 140° to 225°, preferably 150° to 220°.

[0067] In other preferred embodiments, K can be coordinated with C in terms of its steric bulk, provided that C is an aryloxide.

[0068] The term "steric bulk" refers to the spatial extension of C.

[0069] In one embodiment, the steric bulk is increased to decrease K relative to a complex having the same substitution pattern for A, B, and D.

[0070] In other embodiments, the steric bulk is reduced to increase K relative to a complex having the same substitution pattern for A, B, and D.

[0071] In a preferred embodiment, both 1,10-phenanthroline, substituted with respect to electron donating and withdrawing groups, and C characterized with respect to its alkoxide cone angle or aryloxide steric bulk are used to adjust K.

[0072] In accordance with the present invention, when K is within the specified range, it is not necessary to add a Lewis acid, such as zinc chloride, to the complex of formula I to remove the bidentate ligand from the complex and form an activated 14-electron complex from the 18-electron complex. Rather, the complex of formula I is self-activated, i.e., does not require chemical activation.

[0073] In a preferred embodiment, the complex has the formula: [ka] R is C(CH3)3, C(CH3)2C6H5, C6H5, or o-(C 1~4 )-alkoxyC6H4, Preferably, R is o-(C 1~4 )-alkoxyC6H4, More preferably, the complex is [ka] [O-TBS = Ot-butyl-Si(Me)2].

[0074] Complexes 5 to 8 defined in WO2012 / 116695 and complexes III to VI defined in EP 3 268 377 B1 are not self-activated but require chemical activation with a Lewis acid, and therefore can be excluded from item 1, as disclosed in the summary section.

[0075] In a second aspect, the present invention relates to a method for preparing a complex of formula I as defined in any one of the embodiments of the first aspect, comprising: acting on a complex of formula II, [ka] Including, A, B, C, R 3 and R 4 has the meaning given for the complex of formula I relative to 1,10-phenanthroline or substituted 1,10-phenanthroline in the solvent.

[0076] In one embodiment, the method comprises: isolating the complex of formula I in solid form.

[0077] In one embodiment, isolation can be achieved by precipitating the complex of formula I from the solvent, preferably in crystalline form. The complex of formula I can then be isolated by filtration.

[0078] In other embodiments, concentrating the solution essentially results in shifting the equilibrium towards adduct formation.

[0079] Thus, in another embodiment, the method comprises: and isolating the complex of formula I by evaporating the solvent.

[0080] In a third aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: a complex of formula I as defined in any one of the embodiments of the first aspect, and a complex of formula II as defined in the second aspect, and the system includes The complex of formula I and the complex of formula II are dissolved in a solvent.

[0081] This simply means that the complexes of Formula I and Formula II are in equilibrium with each other. This equilibrium is concentration and temperature dependent. Typically, increasing the temperature shifts the equilibrium toward the complex of Formula II. Even more typically, diluting the solution shifts the equilibrium toward the complex of Formula II.

[0082] According to the present invention, the system does not contain a Lewis acid.

[0083] The term "Lewis acid" as used herein includes Lewis acids that are capable of removing 1,10-phenanthroline from any of the complexes defined in WO2012 / 116695 and EP 3 268 377 B1.

[0084] Lewis acids are MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(CF3SO3)2 or Zn(CF3COO)2.

[0085] In a preferred embodiment, the Lewis acid is zinc chloride.

[0086] In a fourth aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: dissolving a complex of formula I as defined in any one of the embodiments of the first aspect in a solvent; The present invention relates to a method for preparing a complex of formula II as defined in a second aspect, comprising:

[0087] In a fifth aspect, the present invention provides a method for producing a pharmaceutical composition comprising: adding a complex as defined in any one of the embodiments of the first aspect to an olefinic compound in the presence of a solvent; The present invention relates to a method for carrying out a metathesis reaction of a compound containing an olefinic double bond, comprising:

[0088] In one embodiment, the compound containing an olefinic double bond is a solvent.

[0089] According to the present invention, the metathesis reaction is carried out in the absence of a Lewis acid.

[0090] Lewis acids are MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(CF3SO3)2 or Zn(CF3COO)2.

[0091] In a preferred embodiment, the Lewis acid is zinc chloride.

[0092] Example Adducts 20-23 in Scheme 1 are representative examples of complexes according to the present invention. They are easy to prepare and isolate starting from the corresponding bispyrrolide precursors. In fact, the isolation and purification of the 14-electron tungsten-alkylidenes 16-19 is extremely difficult and the yields are low, so adduct formation also offers considerable advantages from a synthetic standpoint. [ka] Scheme 1: Synthesis of self-activated 1,10-phenanthroline adducts 20–23

[0093] Dissolving the 18-electron adducts 20–23 releases 1,10-phenanthroline, i.e., the complex dissociates. Under given conditions, the degree of dissociation depends on the stability constant of the adduct, as shown in Scheme 2 below. This example demonstrates how the steric bulk of the alkoxide ligand affects the thermodynamic stability of the adduct; increasing the steric bulk of the ligand decreases the stability constant, resulting in a greater degree of dissociation under the same conditions.

[0094] The equilibrium can be easily controlled over a wide range of physical properties such as concentration and temperature, as elucidated by NMR spectroscopy.

[0095] For example, the stability constant K 22、d6-ベンゼン、298K =615M -1 The unstable (self-activated) complex 22 liberates 34% of the corresponding activated MAP complex 18 in a 0.01 M C6D6 solution. Diluting a solution of 22 in d6-benzene to a concentration of [W] = 0.0025 M liberates 52% of the 14-electron MAP complex.

[0096] Stability constant K 23、d6-ベンゼン、298K =255M -1 The less stable phenanthroline adduct 23, containing 2, dissociates to a greater extent under similar conditions. At 25 °C, a 0.01 M solution of 23 in C6D6 liberates 54% of the active MAP complex 19, and a 10-fold dilution of the solution results in essentially complete liberation of 19.

[0097] It is also important to understand that since the Gibbs free energy of association is near zero (equilibrium) and the entropy change is negative (association), the enthalpy change for adduct formation is expected to be negative (see Gulyas reference above). This means that dissociation of phenanthroline from the 18-electron complex, liberating the 14-electron MAP complex, can be accelerated by increasing the temperature.

[0098] [ka] Scheme 2: Stability constants of self-activated 1,10-phenanthroline adducts 20–23 as a function of the steric bulk of the alkoxide ligand

[0099] Aryloxide ligands have proven to be a very important structural motif in olefin metathesis catalysis. In the design of Schrock catalysts, they generally appear to be superior to alkoxides in terms of both activity and (stereo)selectivity. The "phenanthroline approach" to air-stable, self-activating storage complexes disclosed in this invention can be applied to this class of Schrock catalysts as well.

[0100] MAP24 has proven to be highly active, highly cis-selective, and quite robust in many important cross-metathesis reactions. MAP24 readily reacts with 1,10-phenanthroline. The corresponding adduct 25 can be isolated in very high yields, ranging from 70% to over 98%, depending on the reaction and isolation conditions, as shown in Scheme 3.

[0101] Importantly, unlike previous examples, coordination is not completely stereoselective in the case of 24. Based on the alkylidene coverage of the NMR spectrum of 25, at least two of the possible stereoisomers are formed and exist in solution-phase equilibrium. Both chiral aryloxy ligands or syn-anti isomers of the alkylidene ligands could result in the formation of the observed stereoisomers.

[0102] [ka] Scheme 3: Synthesis and solution-phase behavior of the unstable (self-activated) 1,10-phenanthroline adduct 25

[0103] Complex 25 is self-activated, and its stability constant is highly dependent on the nature of the solvent. Under similar conditions, it dissociates much more readily in CDCl2 than in CD6D6. In CDCl3, dissociation is further accelerated, and at concentrations below 0.01 M at room temperature, the activated MAP complex is virtually completely liberated, as shown by the stability constants in Scheme 3. It also proves that, due to efficient inversion of the phenanthroline coordination, every new alkylidene formed by the interaction between 24 and the bidentate N-heterocycle becomes the stereoisomer of the desired unstable coordination compound.

[0104] Although MAP complex 24 is one of the more robust Schrock catalysts, complexation with 1,10-phenanthroline yielded an adduct with significantly improved stability in air. A 0.01 mmol sample of 24 decomposed quantitatively in air within 2 h, whereas only 5–10% decomposition of 25 was observed over 5 days under similar conditions.

[0105] Finally, complex 25, an air-stable 18-electron storage complex of complex 24, has also proven to be a highly efficient catalyst without the need for Lewis acid activators. Under appropriate conditions, it outperforms 24, particularly in the etherolysis purification of vegetable oils. This catalytic result also demonstrates that phenanthroline is not merely a protective agent but can be an additional tool for tuning and improving catalytic performance.

[0106] The following scheme and table show the effect of the bulkiness of C, expressed in terms of cone angle, on K.

[0107] [ka]

[0108] [Table 1]

[0109] K decreases with increasing cone angle and vice versa, indicating that the bulkiness of C can be used to tune K.

[0110] The self-activated complex 25 was used in the homo-cross metathesis of 9-DAME according to the following scheme: [ka]

[0111] The results are shown in the table below.

[0112] [Table 2]

[0113] In summary, during our research program, we discovered that 1,10-phenanthroline can be efficiently used to synthesize a novel, air-stable, self-activating storage complex for a 14-electron Schrock catalyst. This complexation not only improves air stability but also the overall yield of the catalyst synthesis. The 18-electron phenanthroline adduct can be used directly as a precatalyst for olefin metathesis reactions without the need to remove the phenanthroline from the coordination sphere with a Lewis acid such as zinc chloride. Indeed, phenanthroline may actually function as an additional tool to influence the catalytic performance of the alkylidene complex. [Example]

[0114] Preparation example Example 1: Synthesis of 20

[0115] Bispyrrolide precursor W(CHCMe2Ph)(NAr diCl )(Me2Pyr)2(Ar diClMe2Pyr = 2,6-dichlorophenyl, Me2Pyr = 2,5-dimethylpyrrolide (137.4 mg, 0.207 mmol) was dissolved in toluene (10 mL) and the solution was cooled to -30 °C in a double-jacketed reactor. PhMe2COH (28 mg, 0.207 mmol) was added as a solid. Alcohol residues from the walls of the vial were washed into the reaction mixture with toluene (4 × 0.5 mL). The reaction mixture was stirred at -30 °C overnight. 1 H NMR analysis showed complete conversion to 16. The reaction mixture was warmed to 0°C and 1,10-phenanthroline (37.4 mg, 0.207 mmol) was added. The reaction mixture turned deep red. It was stirred without cooling for 6 h, allowing the temperature to reach room temperature. 1 H NMR analysis indicated equilibrium between the MAP complex and its phenanthroline adduct. The solvent was removed and the solid residue was stirred with pentane. The suspension was transferred to a freezer for 2-3 hours, after which the product was isolated by filtration on a frit pre-cooled in the freezer. A tan solid. Yield: 152 mg (83%).

[0116] 16 NMR properties: 1 H-NMR(C6D6): δ1.50(s,3H,CH3),1.56(s,3H,CH3),1.57(s,3H,CH3),1.63(s,3H,CH3),2.34(s,6H,CH3Me2Pyr),6.16(s br,2H,CHMe2Pyr),6.26(t,1H,N-ArC パラ -H), 8.61 ppm (s, 1H, W=CH, 2 J WH =16.0Hz).

[0117] 20 NMR properties: 1 H-NMR (C6D6): δ 0.63 (s, 3H, CH3), 0.98 (s, 3H, CH3), 1.94 (s, 3H, CH3 neophyllidene), 2.18 (s, 3H, CH3 neophyllidene), 2.88 (br, 6H, CH3Me2Pyr), 6.04 (t, 3 J HH =8.0Hz,1H,N-ArC パラ -H), 6.55(dd,J HH=8.1,4.9Hz,1H,C3-H PHEN),6.68(dd,J HH =8.1,5.1Hz,1H,C3'-H PHEN),6.74-7.41(m,16H,C メタ -Hneophilidene,C パラ -H Neophyllidene, CH MePyr, N-Ar C メタ -H,C4-H,C4'-H,C5-H,C5'-H PHEN,alkoxyPh),7.73(m,2H,C オルト -H),8.99(dd,J HH =5.1,1.4Hz,1H,C2'-H PHEN),9.36(dd,J HH =4.9,1.4Hz,1H,C2-H PHEN),12.02ppm(s, 2 J WH =10.0Hz,1H,W=CH).

[0118] Example 2: Synthesis of 21

[0119] The bispyrrolide precursor W(CHCMePh)(NAr) dissolved in benzene (3 mL) diCl )(Me2Pyr)2(Ar diCl The corresponding alcohol (0.25 mmol) dissolved in benzene (1 mL) was slowly added to the reaction mixture (Me2Pyr = 2,6-dichlorophenyl, Me2Pyr = 2,5-dimethylpyrrolide) (166 mg, 0.25 mmol) while stirring at room temperature. The progress of the reaction was monitored by the 1 H NMR analysis confirmed the reaction. In a NMR yield of >98% for 17, 1,10-phenanthroline (0.25 mmol) dissolved in benzene (approximately 2 mL) was added in situ and the reaction mixture was stirred for 1 h. The solvent was removed in vacuo, the residue was dissolved in toluene, and the product was isolated by crystallization in a freezer (-38 °C) from a mixture of toluene and pentane. Brownish-yellow solid. Yield: 160 mg (74%).

[0120] 17 NMR properties: 1 H-NMR (300 MHz, C6D6): δ 0.65 (t, 3 J HH=7.4Hz,3H,CH2CH3),0.70(t, 3 J HH =7.4Hz, 3H, CH2CH3), 1.66(s, 3H, CH3neophyllidene), 1.72(s, 3H, CH3neophyllidene), 1.74-1.90(m, 4H, CH2CH3), 2.39(s, 6H, CH3Me2Pyr), 6.15(s br, 2H, CH Me2Pyr), 6.28(t, 3 J HH =8.1Hz, 1H, N-Ar C パラ -H),6.91(d, 3 J HH =8.1Hz, N-Ar C メタ -H), 6.96(m, 1H, C パラ -H neophyllidene), 7.03 (m, 1H, -OC(C2H5)-Ph C パラ -H), 7.08-7.23(m,6H,C メタ -Hneophyllidene,OC(C2H5)-Ph C オルト -H,OC(C2H5)-Ph C メタ -H), 7.44(m,2H,C オルト -H neophyllidene), 9.12 ppm (s, 1H, W=CH, 2 J WH =16.0Hz).

[0121] 21 NMR properties: 1 H-NMR (C6D6): δ 0.22 (t, 3 J HH =7.4Hz,3H,CH2CH3),0.41(t, 3 J HH =7.4Hz, 3H,CH2CH3), 0.69(m,1H,CH2CH3), 1.09(m,1H,CH2CH3), 1.49(m,2H,CH2CH3), 2.00(s,3H,CH3neophyllidene), 2.22(s,3H,CH3neophyllidene), 2.74(w br,3H,CH3Me2Pyr), 3.21(w br,3H,CH3Me2Pyr), 6.04(t, 3 J HH =8.0Hz, 1H, N-Ar C パラ-H),6.43-6.68(m,7H,C3-H,C3'-H,C4'-H,C5-H,C5'-H PHEN,C パラ -Hneophyllidene, -OC(C2H5)-Ph C パラ -H),6.79(s br,2H,CH Me2Pyr),6.86-6.94(m,N-Ar C メタ -H), 7.08-7.21(m, 4H, C メタ -H,C オルト -H),7.25(dd,J HH =7.9,1.2Hz,1H,C4-H PHEN),7.32(m,2H,C メタ -H), 7.73(m,2H,C オルト -H),8.87(dd,J HH =5.0,1.2Hz,1H,C2-H PHEN),9.17(dd,J HH =4.8,1.3 Hz,1H,C2-H PHEN),12.09ppm(s, 2 J WH =10.0Hz,1H,W=CH).

[0122] Example 3: Synthesis of 22

[0123] The bispyrrolide precursor W(CHCMePh)(NAr) dissolved in benzene (6 mL) diCl )(Me2Pyr)2(Ar diCl To Me2Pyr (2,6-dichlorophenyl, Me2Pyr = 2,5-dimethylpyrrolide) (296 mg, 0.45 mmol) was added dicyclopropyl(paratolyl)methanol (0.45 mmol) dissolved in benzene (2 mL). The reaction mixture was stirred for 4 hours. 1 H NMR analysis showed complete conversion to 18. 1,10-Phenanthroline (0.45 mmol) dissolved in benzene (ca. 4 mL) was added in situ and the reaction mixture was stirred for 1 h. The solvent was removed in vacuo and the residue was triturated with pentane to give a brownish-yellow solid, which was then filtered, washed with pentane, and dried in vacuo. Yield: 305 mg (77%).

[0124] 18 NMR properties: 1H-NMR (C6D6) δ (ppm): 0.1-0.7 (m, 8H, CH2-cyclopropyl), 0.95-1.1 (m, 2H, CH-cyclopropyl), 1.58 (s, 3H, CH3), 1.66 (s, 3H, CH3), 2.13 (s, 3H, Ar-CH3), 2.33 (s, 12H, CH3), 6.17 (s, 2H, =CHMe2Pyr), 6.27 (t, 1H, N-Ar C パラ -H),6.85-7.13(m,10H,aromatic),7.33(m,2H,C オルト -H neophyllidene), 7.44 (m, 2H, C オルト -H benzyl), 8.67(s, 2 J WH =15.3Hz,1H,W=CH).

[0125] NMR properties of 22: 1 H-NMR (C6D6): δ -1.70 (m, 1H, CH2-cyclopropyl), -0.86 (m, 2H, CH2-cyclopropyl), -0.65 (m, 1H, CH2-cyclopropyl), -0.52 (m, 1H, CH2-cyclopropyl), -0.40 (m, 1H, CH2-cyclopropyl), -0.23 (m, 1H, CH2-cyclopropyl), 0.16 (m, 1H, CH2-cyclopropyl), 1.24 (m, 2H, CH-cyclopropyl), 1.96 (s, 3H, CH3-neophyllidene), 2.16 (s, 3H, CH3), 2.18 (s, 3H, CH3), 2.81 (w br, 6H, CH3Me2Pyr), 6.06 (t, 3 J HH =8.0Hz, 1H, N-Ar C パラ -H),6.57(dd,J HH =8.2,5.0Hz,1H,C3-H PHEN),6.78(dd,J HH =8.2,5.2Hz,1H,C3'-H PHEN),6.87-7.47(m,13H,C4-H,C4'-H,C5-H,C5'-H PHEN,C メタ -Hneophilidene,C パラ -H Neophyllidene, CH MePyr, N-Ar C メタ -H,C メタ -H), 7.52(m,2H,C オルト-H), 7.67(m,2H,C オルト -H),9.20(dd,J HH =5.2,1.5Hz,1H,C2'-H PHEN),9.58(dd,J HH =5.0,1.5Hz,1H,C2-H PHEN),12.07ppm(s, 2 J WH =10.0Hz,1H,W=CH).

[0126] A 0.01 M solution of self-activated complex 22 contained 33% of complex 18 liberated in C6D6 at 298 K. A 0.0025 M solution of isolated self-activated complex 22 contained 52% of complex 18 liberated in C6D6 at 298 K.

[0127] Example 4: Synthesis of 23

[0128] The bispyrrolide precursor W(CHCMePh)(NAr) dissolved in benzene (3 mL) diCl )(Me2Pyr)2(Ar diCl To Me₂Pyr (2,6-dichlorophenyl, Me₂Pyr = 2,5-dimethylpyrrolidone) (141 mg, 0.2125 mmol) was added Ph₃COH (55 mg, 0.2125 mmol, 0.85 equiv.) as a solid, and residue from the vial walls was washed into the reaction mixture with benzene (2 mL). The reaction mixture was stirred at room temperature for 1 hour. 1 H NMR analysis showed complete conversion to 19. No excess alcohol was detected. 1,10-Phenanthroline (38 mg, 0.2125 mmol) was added and the reaction mixture was stirred at room temperature for 30 min. 1 H NMR analysis indicated equilibrium between the MAP complex and its phenanthroline adduct. All volatiles were removed in vacuo. The residue was triturated with pentane to give the product as a brownish-yellow powder. It was isolated by filtration, washed with a small amount of cold pentane, and dried in vacuo. Yield: 182 mg (87%).

[0129] 19 NMR properties: 1H-NMR (300 MHz, CD): δ 1.58 (s, 3H, CH3 neophyllidene), 1.60 (s, 3H, CH3 neophyllidene), 2.24 (s, 6H, CH3 Me2 Pyr), 6.04 (s br, 2H, CH3 Me2 Pyr), 6.28 (t, 3 J HH =8.1Hz,1H,C パラ -H N-Ar), 6.91(d, 3 J HH =8.1Hz,C メタ -H N-Ar), 6.93 (m, 1H, C パラ -H neophyllidene), 6.97-7.10 (m, 11H, C メタ -H OC(Ph)3,C パラ -H OC(Ph)3,C メタ -H neophyllidene), 7.25-7.34 (m, 8H, C オルト -H OC(Ph)3,C オルト -H neophyllidene), 7.92 ppm (s, 1H, W=CH, 2 J WH =16.5Hz).

[0130] 23 NMR properties: 1 H-NMR (C6D6): δ 1.96 (s, 3H, CH3 neophyllidene), 2.05 (s, 3H, CH3 neophyllidene), 2.54 (s, 3H, CH3Me2Pyr), 2.87 (s, 3H, CH3Me2Pyr), 5.98 (t, 3 J HH =8.1Hz, 1H, N-Ar C パラ -H), 6.50(dd,J HH =8.2,4.9Hz,1H,C3-H PHEN),6.57(dd,J HH =8.0,5.2Hz,1H,C3'-H PHEN),6.33-7.41(m,24H,C メタ -Hneophilidene,C パラ -H Neophyllidene, CH MePyr, N-Ar C メタ -H,C4-H,C4'-H,C5-H,C5'-H PHEN, aryloxy Ph), 7.52 (m, 2H, C オルト -H), 7.76(m,2H,C オルト-H),8.77(dd,J HH =5.2,1.4Hz,1H,C2'-H PHEN),9.49(dd,J HH =4.9,1.5 Hz,1H,C2-H PHEN),12.29ppm(s, 2 J WH =10.5Hz,1H,W=CH).

[0131] A 0.01 M solution of the self-activated complex 23 contained 54% of the complex 19 liberated in C6D6 at 298 K. A 0.001 M solution of the isolated self-activated complex 23 contained more than 95% of the complex 19 liberated in C6D6 at 298 K.

[0132] Example 5: Synthesis of 25; Synthetic Procedure A

[0133] 24 (899 mg, 0.8 mmol) and 1,10-phenanthroline (144 mg, 0.8 mmol) were dissolved in benzene (15 mL), and the reaction mixture was stirred at room temperature. The orange product began to crystallize within 2 hours, eventually becoming a thick suspension. The reaction mixture was stirred overnight at room temperature. The product was isolated by filtration and washed with pentane. It was first dried on a frit under a vacuum-induced nitrogen stream. It was transferred to a tared vial and further dried under high vacuum at room temperature. A light orange powder. Yield: 807 mg (77%). There is one single structural isomer, but it is a mixture of stereoisomers.

[0134] Example 5: Synthesis of 25; Synthetic Procedure B

[0135] 24 (674 mg, 0.6 mmol) and 1,10-phenanthroline (108 mg, 0.6 mmol) were dissolved in benzene (10 mL), and the reaction mixture was stirred at room temperature. The orange product began to crystallize within 2 hours and gradually turned into a thick orange suspension. Evaporation of the benzene in vacuo gave the product as an orange solid. Yield: quantitative. There is one single structural isomer, but it is a mixture of stereoisomers. (The NMR characteristics of the products obtained by procedures A and B are identical.)

[0136] 25 selected NMR data: 1 H-NMR (C6D 6, δ ref 1H溶媒 = 7.16 ppm): 13.19 ppm (broad s, 1H, W = CH, major structural isomer); 12.99 (broad s, 1H W = CH, minor structural isomer).

[0137] Compound 25 contained less than 2% ArOH (C6D6, 0.01M, 298K).

[0138] After 5 days in contact with air, compound 25 contained approximately 5% ArOH (C6D6, 0.01M, 298K).

[0139] Example 6: HCM of 9DAME using complex 25

[0140] Substrate purification of 9-DAME by adsorption treatment: The substrate was filtered three times onto basic aluminum oxide (20 wt%).

[0141] Under glovebox conditions, the substrate was pipetted into a dry 4 mL vial, followed by the catalyst stock solution. The vial was closed with a perforated cap, and the reaction mixture was stirred at room temperature. A sample was then taken, dissolved in EtOAc (Suprasolv® for GC), and analyzed by GCMS to determine the conversion.

[0142] A GCMS-FID system: Shimadzu 2010Plus, split injection type, column: Zebron ZB-35HT INFERNO, 30 m x 0.25 mm x 0.25 μm was used for the analysis of the starting material and product mixture.

[0143] The reactions were carried out using complexes 24 and 25 as catalysts, and the results are shown in the table below.

[0144] [Table 3]

[0145] Example 7: Ethenolysis of FAME

[0146] In a nitrogen-filled glovebox, fatty acid methyl esters were weighed into 30 mL glass vials and mixed with a stock solution of triethylaluminum (23 wt % in toluene). The optimal amount of triethylaluminum was previously determined and found to be 700 ppm. The mixture was stirred at room temperature for 1 h. Catalyst 25 was added as a stock solution (0.01 M in benzene). The vials were placed in a stainless steel autoclave equipped with an alublock and stirred at 50 °C for 18 h under 10 atm of ethylene gas overpressure. Five reactions were carried out in the same autoclave with a common gas space. Excess ethylene was vented. 2.0 μl of the reaction mixture was removed, diluted to 1.5 mL with n-pentane, and analyzed by GCMS-FID (Shimadzu 2010 Plus, Zebron ZB-35HT INFERNO, 30 m x 0.25 mm x 0.25 μm column).

[0147] The results are shown in the table below.

[0148] [Table 4]

[0149] Example 8: Synthesis of Complex A1 [ka]

[0150] Bispyrrolide precursor Mo(CHCMe2Ph)(NAr diiPr )(Me2Pyr)2(Ar diiPrMe2Pyr = 2,6-diisopropylphenyl, Me2Pyr = 2,5-dimethylpyrrolide (118 mg, 0.2 mmol) was dissolved in benzene (2 mL). Ph(CF3)2COH (30 μL, 43.6 mg, 0.179 mmol) was added. The reaction mixture was stirred at room temperature overnight. NMR analysis confirmed the formation of the desired MAP complex along with a small amount of the corresponding bisalkoxide complex as a by-product. 1,10-Phenanthroline (32.3 mg, 0.179 mmol) was added to the reaction mixture. Residual phenanthroline was rinsed from the vial into the reaction mixture with a small amount of benzene (approximately 1 mL total). The reaction mixture was stirred at room temperature for 1 hour, and then all volatiles were evaporated in vacuo. The residue was triturated with pentane to give the product as an orange powder, which was isolated by filtration and dried in vacuo. Orange solid. Yield: 151 mg (92%). 1 H NMR: 15.03 ppm; 19 F NMR: -69.78(q), -75.87(q) ppm. 1 For H NMR (C6D6), see Figure 2.

[0151] Example 9: Synthesis of Complex A2

[0152] [ka]

[0153] Bispyrrolide precursor Mo(CHCMe2Ph)(NAr diiPr )(Me2Pyr)2(Ar diiPrMe2Pyr (=2,6-diisopropylphenyl, Me2Pyr=2,5-dimethylpyrrolide) (118 mg, 0.2 mmol) was dissolved in toluene (3 mL). This solution was transferred to a glovebox freezer, cooled to -30 °C, and allowed to stand. A toluene solution of Ph(CF3)2COH (0.7 mL, 0.12 M, 0.084 mmol), pre-cooled in a freezer at -30 °C, was added to the Mo-bispyrrolide precursor solution. The reaction mixture was homogenized by hand stirring for a few seconds and then placed in the freezer without stirring. After 1 h, another portion of the Ph(CF3)2COH solution (0.7 mL, 0.12 M, 0.084 mmol) was added, and the reaction mixture was placed in the freezer without stirring for another 1 h. The reaction mixture was then removed from the freezer and stirred at room temperature for 3 h. NMR analysis revealed that the reaction mixture contained both unreacted Mo-bispyrrolide and alcohol. The mixture was stirred overnight at room temperature and analyzed again by NMR. The alcohol was consumed, leaving approximately 8% of the bispirolide unreacted. The reaction mixture was cooled to -30 °C, and the third portion of Ph(CF3)2COH solution (0.110 mL, 0.12 M, 0.0132 mmol) was added. The reaction mixture was placed in the freezer for 1 h and then stirred at room temperature for 6 h. NMR analysis revealed that the Mo-bispyrrolide content had decreased to approximately 3%. 4,7-Dichloro-1,10-phenanthroline (47.1 mg, 0.189 mmol; carefully dried over molecular sieves in DCM) was added to the MAP complex solution. The reaction mixture turned a deep reddish-brown color. The phenanthroline residue was washed into the reaction mixture from the vial with a small amount of toluene (2 × 0.5 mL). The reaction mixture was stirred until the dichlorophenanthroline was completely dissolved (approximately 30 min), after which all volatiles were evaporated in vacuo. The residue was triturated with pentane to give the product as a tan solid. It was isolated by filtration and washed with pentane. It was dried first in a vacuum induced argon stream and then in vacuo. Tan solid. Yield 95 mg (53%). 1 H NMR: 14.96 ppm; 19 F NMR: -69.78(q), -75.87(q) ppm. 1For H NMR (C6D6), see Figure 3.

[0154] Example 10: Synthesis of Complex A3

[0155] [ka]

[0156] Bispyrrolide precursor Mo(CHCMe2Ph)(NAr diiPr )(Me2Pyr)2(Ar diiPr Me2Pyr (2,6-diisopropylphenyl, Me2Pyr = 2,5-dimethylpyrrolide) (59 mg, 0.1 mmol) was dissolved in toluene (2 mL). This solution was transferred to a glovebox freezer, cooled to -30 °C, and allowed to stand. A toluene solution of Ph3SiOH (27.6 mg, 0.1 mmol in 2 mL of toluene), pre-cooled to -30 °C in a freezer, was added to the Mo-bispyrrolide precursor solution. The reaction mixture was homogenized by hand stirring for a few seconds and then left in the freezer without stirring for 48 h. NMR analysis confirmed the complete and selective conversion of the Mo-bispyrrolide precursor to the desired MAP complex. 1,10-Phenanthroline (17.1 mg, 0.095 mmol) dissolved in toluene (1 mL) was added to the reaction mixture. Residual phenanthroline was rinsed from the vial into the reaction mixture with a small amount of benzene (approximately 1 mL total). The reaction mixture was stirred at room temperature for 1 hour, and then all volatiles were evaporated in vacuo. The residue was triturated in pentane to give the product as a dark yellow powder. It was isolated by filtration and dried in vacuo. A dark yellow solid. Yield: 68 mg (75%). 1 H NMR: 15.54 ppm. 1 For H NMR (C6D6), see Figure 3.

Claims

1. A composition comprising a solvent and a complex of formula I, 【Chemistry 1】 M=Mo or W; A is N-R １ or O, and R １ are optionally each independently substituted with one or more of C 1-10 alkyl, C 1-10 alkoxy, phenyl, halogen, CN, and CF 3 . １～１０ is alkyl or aryl, B is selected from pyrrole and pyrazole, each optionally and independently substituted with one or more of C 1-10 alkyl, C 1-10 alkoxy, or phenyl; or B is C, C is O-R ２ and R ２ is independently selected from C 1-10 alkyl substituted with one or more of halogen or phenyl; or a substituted phenyl independently substituted with one or more of C 1-10 alkyl, C 1-10 alkyl substituted with one or more halogens, C 1-10 alkoxy, phenyl, halogen, —(CH 2 ) 4 — which forms a cyclic ring together with said phenyl, or —(CH═CH—CH═CH)— which forms a cyclic ring together with said phenyl, or a phenyl substituted with —O-silyl; D is a neutral bidentate ligand, said ligand being 1,10-phenanthroline or a substituted 1,10-phenanthroline, wherein the phenanthroline is substituted with one or more electron-donating substituents independently selected from C 1-10 alkyl, C 1-10 alkoxy, and phenyl; or substituted with one or more electron-withdrawing substituents selected from halogen, CN, CF3 and CCl3; R ３ and R ４ However, independently, H, C １～１０ alkyl or aryl, C １～１０ The alkyl and aryl are optionally substituted with one or more of C 1-5 alkyl, C 1-5 alkyl substituted with one or more halogens, C 1-5 alkoxy, phenyl, halogen, and R ３ and R ４ is hydrogen, a compound of formula I is dissolved in the solvent to liberate the bidentate ligand D upon dissociation to form a compound of formula II, the compound of formula II having catalytic activity in olefin metathesis reactions; 【Chemistry 2】 the stability constant K of said complex of formula I is in the range of 5 L*mol −1 to 250,000 L*mol −1 when measured at 298 K when said complex of formula I is dissolved in said solvent; the composition does not contain a Lewis acid for removing the neutral bidentate ligand D from the compound of formula I to liberate a compound of formula II; composition.

2. K is 10L ＊ mol －１ ~150,000L ＊ mol －１ or 10L ＊ mol －１ ~100,000L ＊ mol －１ or 10L ＊ mol －１ ~50,000L ＊ mol －１ or 10L ＊ mol －１ ~10,000L ＊ mol －１ or 10L ＊ mol －１ ~5000L ＊ mol －１ or 10L ＊ mol －１ ~500L ＊ mol －１ The composition of claim 1, wherein the

3. 3. The composition according to claim 1, wherein the concentration of the complex in the solvent ranges from 0.0001 to 0.5 M.

4. The complex of claim 1, wherein 【Transformation 3】 R is C(CH 3 ) 3 , C(CH 3 ) 2 C 6 H 5 , C 6 H 5 , or o-(C 1-4 )-alkoxyC 6 H 4 ; [O-TBS=O-Si(t-butyl)(Me) 2 ], The composition according to any one of claims 1 to 3.

5. The composition of claim 4, wherein R is o-(C 1-4 )-alkoxyC 6 H 4 .

6. The complex 【Chemistry 4】 The composition according to claim 4 or 5,

7. 1. A method for conducting a metathesis reaction of a compound containing an olefinic double bond, comprising: adding the composition of any one of claims 1 to 6 to the olefinic compound in the presence of the solvent; A method comprising:

8. The method of claim 7 , wherein the compound containing an olefinic double bond is the solvent.

9. The complex has the formula: 【Transformation 5】 R is C(CH ３ ) ３ , C(CH ３ ) ２ C ６ H ５ , C ６ H ５ , or o-(C １～４ )-alkoxy C ６ H ４ and [O-TBS=O-Si(t-butyl)(Me) ２ ], Complex.

10. The complex of claim 9, wherein R is o-(C 1-4 )-alkoxyC 6 H 4 .

11. The complex of claim 1 【Transformation 6】 11. The complex according to claim 9 or 10, wherein

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