Halogen-containing metathesis catalysts and methods thereof

A method for performing an alkene metathesis reaction, comprising:

• reacting a first species comprising a first carbon to carbon double bond with a second species comprising a second carbon to carbon double bond in the presence of a compound of formula I-a, to provide at least one product comprising a third carbon to carbon double bond, wherein:
• a carbon atom of the first carbon to carbon double bond in the first species is substituted with a first substituent selected from halogen and optionally substituted C1-6 haloalkyl;
• and
• the third carbon to carbon double bond in the at least one product comprises a carbon atom of the first carbon to carbon double bond and a carbon atom of the second carbon to carbon double bond, wherein the carbon atom of the first carbon to carbon double bond is substituted with the first substituent;
• wherein each carbon atom of the first carbon to carbon double bond in the first species is independently substituted with the first substituent;
• wherein the first species is
• wherein each of X and Y is independently halogen or independently optionally substituted C1-6 haloalkyl;
• or
• wherein
• is cis-1,2-dichloroethene or cis 1,2-dibromoethene or cis-1,1,1,4,4,4-hexafluoro-2-butene;
• or
• wherein a carbon atom of the first carbon to carbon double bond in the first species is independently substituted with an optionally substituted C1-6 haloalkyl group, and the at least one product comprises a third carbon to carbon double bond substituted with the optionally substituted C1-6 haloalkyl group, and wherein the optionally substituted C1-6 haloalkyl is methyl substituted with one to three halogens, wherein the optionally substituted C1-6 haloalkyl comprises one or more —F;
• or wherein the optionally substituted C1-6 haloalkyl is methyl substituted with one to three halogens, wherein at least one halogen is —F;
• or wherein the optionally substituted C1-6 haloalkyl is —CH2F, —CHF2, —CClF2, —CF3, —C2F5, —C3F7, —C4F9, —C5F11, or —C6F13;
• wherein the alkene metathesis reaction is a Z-selective cross-metathesis reaction or a Z-selective ring-opening cross metathesis reaction;
• and
• wherein the compound of formula I-a is:
• M is molybdenum;
• wherein:
• R1 is adamantyl, tert-butyl, 2,6-dichlorophenyl, 2,6-dibromophenyl, 2,6-dimethylphenyl, 2,6-di-t-butylphenyl, 2,6-diisopropylphenyl, or pentafluorophenyl;
• one of R2 and R3 is hydrogen and the other is —C(Me)3 or is —C(Me)2Ph or is phenyl or 2-methoxyphenyl or 2-isopropoxyphenyl;
• R4 is 2,6-(2,6-dimethylphenyl)2C6H3, 2,6-(mesityl)2C6H3, 2,6-(2,6-diethylphenyl)2C6H3, 2,6-(2,4,6-triethylphenyl)2C6H3, 2,6-(2,6-diisopropylphenyl)2C6H3, 2,6-(2,4,6-triisopropylphenyl)2C6H3, 2,6-(2,6-di-t-butylphenyl)2C6H3, 2,6-(2,4,6-tri-t-butylphenyl)2C6H3, 2,6-(2,6-diphenylphenyl)2C6H3, 2,6-(2,4,6-triphenylphenyl)2C6H3, 2,6-(3,5-di-t-butylphenyl)2C6H3, 2,6-(2,6-dichlorphenyl)2C6H3, 2,6-(2,4,6-trichlorophenyl)2C6H3, 2,4,6-(mesityl)3C6H2, 2,3,5,6-(phenyl)4C6H, or 2,3,4,5,6-(phenyl)5C6;
• R5 is —Cl or Br;
• R6 is selected from the group consisting of an ether, a nitrile, a phosphine, a pyridine, and an amine;
• and
• n is 0-2.