One-pot synthesis of group 8 transition metal carbene complexes useful as olefin metathesis catalysts

A method for synthesizing a ligand precursor having the structure of formula (XI):

• in which R3, R4, R8, R8A, R9, and R9A are substituents independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and -(Z)n-Fn where n is zero or 1, Z is Z is hydrocarbylene, substituted hydrocarbylene and/or heteroatom-containing hydrocarbylene, and Fn is phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C1-C20 alkylsulfanyl, C5-C20 arylsulfanyl, C1-C20 alkylsulfonyl, C5-C20 arylsulfonyl, C1-C20 alkylsulfinyl, C5-C20 arylsulfinyl, sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C5-C20 aryloxycarbonyl, carboxyl, carboxylato, mercapto, formyl, C1-C20 thioester, cyano, cyanato, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, halogen, stannyl, or germyl, any of which, if the substituent permits, may be further substituted with additional hydrocarbyl and/or -(Z)n-Fn moieties, and further wherein any two or more of R3, R4, R8, R8A, R9, and R9A are optionally linked to form a cyclic group,
• wherein the method comprises:
• contacting a compound having the structure of formula (XII):
• with chloroform and a non-nucleophilic base effective to deprotonate the chloroform, wherein, in formula (XII), X− is an anionic counterion.

A method for synthesizing a transition metal alkylidene complex of formula (XIV):

• wherein M is Ru or Os, X1 and X2 are anionic ligands, L is P(R5R6R7), R5, R6, and R7 are each independently aryl or C1-C10 alkyl, R, R1 and R2 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and -(Z)n-Fn where n is zero or 1, Z is a hydrocarbylene linkage, and Fn is a functional group, and R3, R4, R8, R8A, R9, and R9A are substituents independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and -(Z)n-Fn, wherein the method comprises:
• (a) contacting the ligand precursor (XI):
• with M(X1)2(L4)2, wherein L4 is an eta-6 coordinating ligand, to provide the intermediate (XV):
• (b) contacting intermediate (XV) with P(R5R6R7) in the presence of hydrogen and a base, to give the dihydrogen complex (XVI):
• (d) thereafter treating the dihydrogen complex (XVI) with an alkyne of the formula (VIII):
• wherein R, R1, R2 and X2 are as defined previously.

A method for synthesizing a transition metal vinylidene complex of formula (XVII):

• wherein M is Ru or Os, X1 and X2 are anionic ligands, R13 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and -(Z)n-Fn where n is zero or 1, Z is a hydrocarbylene linkage, and Fn is a functional group, and R3, R4, R8, R8A, R9, and R9A are substituents independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and -(Z)n-Fn, wherein the method comprises:
• (a) contacting the ligand precursor (XI):
• with MX1X2(L4)2, wherein L4 is an eta-6 coordinating ligand, to provide the intermediate (XV):
• thereafter treating intermediate (XIV) with an alkyne of the formula H—C≡C—R13.