Halogen-containing metathesis catalysts and methods thereof

1. 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 C 1-6 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 C 1-6 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 C 1-6 haloalkyl group, and the at least one product comprises a third carbon to carbon double bond substituted with the optionally substituted C 1-6 haloalkyl group, and wherein the optionally substituted C 1-6 haloalkyl is methyl substituted with one to three halogens, wherein the optionally substituted C 1-6 haloalkyl comprises one or more —F; or wherein the optionally substituted C 1-6 haloalkyl is methyl substituted with one to three halogens, wherein at least one halogen is —F; or wherein the optionally substituted C 1-6 haloalkyl is —CH 2 F, —CHF 2 , —CClF 2 , —CF 3 , —C 2 F 5 , —C 3 F 7 , —C 4 F 9 , —C 5 F 11 , or —C 6 F 13 ;

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:

R 1 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 R 2 and R 3 is hydrogen and the other is —C(Me) 3 or is —C(Me) 2 Ph or is phenyl or 2-methoxyphenyl or 2-isopropoxyphenyl;

R 4 is 2,6-(2,6-dimethylphenyl) 2 C 6 H 3 , 2,6-(mesityl) 2 C 6 H 3 , 2,6-(2,6-diethylphenyl) 2 C 6 H 3 , 2,6-(2,4,6-triethylphenyl) 2 C 6 H 3 , 2,6-(2,6-diisopropylphenyl) 2 C 6 H 3 , 2,6-(2,4,6-triisopropylphenyl) 2 C 6 H 3 , 2,6-(2,6-di-t-butylphenyl) 2 C 6 H 3 , 2,6-(2,4,6-tri-t-butylphenyl) 2 C 6 H 3 , 2,6-(2,6-diphenylphenyl) 2 C 6 H 3 , 2,6-(2,4,6-triphenylphenyl) 2 C 6 H 3 , 2,6-(3,5-di-t-butylphenyl) 2 C 6 H 3 , 2,6-(2,6-dichlorphenyl) 2 C 6 H 3 , 2,6-(2,4,6-trichlorophenyl) 2 C 6 H 3 , 2,4,6-(mesityl) 3 C 6 H 2 , 2,3,5,6-(phenyl) 4 C 6 H, or 2,3,4,5,6-(phenyl) 5 C 6 ;

R 5 is —Cl or Br;

R 6 is selected from the group consisting of an ether, a nitrile, a phosphine, a pyridine, and an amine; and

n is 0-2.

2. The method of claim 1 , wherein the method is performed in the presence of a compound selected from the group consisting of: trityl tetrakis(pentafluorophenyl)borate [(C 6 H 5 ) 3 CB(C 6 F 5 ) 4 ], sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate [Na(B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 )], tris(pentafluorophenyl)boron [B(C 6 F 5 ) 3 ], dimethylanilinium tetrakis(pentafluorophenyl) borate [PhNMe 2 HB(C 6 F 5 ) 4 ], and CuCI.

3. The method of claim 1 , wherein the compound of formula I-a is selected from:

Mo(NAd)(CHCMe 2 Ph)(OHMT)(Br)(py), Mo(NAd)(CHR)(OHMT)(Cl)(py), Mo(NAd)(CHR)(OHMT)(Br)(MeCN), Mo(NAd)(CHR)(OHMT)(Cl)(MeCN), Mo(NC 6 F 5 )(CHR)(OHMT)(Br)(py), Mo(NC 6 F 5 )(CHR)(OHMT)(Cl)(py), Mo(N-t-Bu)(CHCMe 2 Ph)(OHMT)(Cl)(MeCN), Mo(N-t-Bu)(CHCMe 2 Ph)(OHIPT)(Cl)(MeCN), Mo(N-t-Bu)(CHCMe 2 Ph)(OTBT)(Cl)(MeCN), Mo(NAd)(CHR)(OHMT)(Br), Mo(NAd)(CHR)(OHMT)(Cl)(ADNH 2 ), Mo(N-t-Bu)(CHt-Bu)(OHMT)(Cl)(MeCN), Mo(N-t-Bu)(CHt-Bu)(OHMT)(Br)(MeCN), Mo(N-t-Bu)(CHt-Bu)(OHIPT)(Cl)(MeCN), Mo(NC 6 F 5 )(CHR)(OHMT)(Cl)(PhMe 2 P), Mo(NC 6 F 5 )(CHR)(OHIPT)(Cl)(PhMe 2 P), and Mo(NC 6 F 5 )(CHR)(OHMT)(Cl)(Me 3 P),

wherein Ad is adamant-1-yl, AdNH 2 is 1-amino-adamantane, py is pyridine, Ph is phenyl, Me is methyl, R is —CMe 2 Ph, OHMT is O-2,6-(mesityl) 2 C 6 H 3 , OHIPT is O-2,6-(2,4,6-(i-Pr) 3 C 6 H 2 ) 2 C 6 H 3 , and OTBT is O-2,6-(3,5-(di-t-Bu-phenyl) 2 C 6 H 3 ).