Air-stable ni(0)-olefin complexes and their use as catalysts or precatalysts
The present invention relates to air stable, binary Ni(0)-olefin complexes and their use in organic synthesis.
1 . An air-stable Ni(R) 3 —complex wherein Ni represents Ni(0) and R is the same or different and represents a trans-stilbene of the Formula (I):
wherein in Formula (I), R 3 and R 8 are the same or different and are selected from C 1 to C 8 perfluoro alkyl and the others of R 1 to R 10 are hydrogen, and R 11 to R 12 may be the same or different and are selected from H, C 1 to C 6 alkyl, O—C 1 to C 6 alkyl, C 3 to C 6 cycloalkyl, or —O—C 3 to C 6 cycloalkyl; or,
wherein in Formula (I), R 3 and R 8 are each C 1 to C 8 perfluoro alkyl and the others of R 1 to R 10 and R 11 to R 12 are hydrogen; or,
wherein in Formula (I), R 3 and R 8 are each —CF 3 , and the others of R 1 to R 10 and R 11 to R 12 are hydrogen.
2 . Process for preparing an air-stable Ni(R) 3 —complex wherein Ni represents Ni(0) and R are the same or different and represents a trans-stilbene of the Formula (I):
wherein in Formula (I), R 3 and R 8 are the same or different and are selected from C 1 to C 8 perfluoro alkyl and the others of R 1 to R 10 are hydrogen, and R 11 to R 12 may be the same or different and are selected from H, C 1 to C 6 alkyl, O—C 1 to C 6 alkyl, C 3 to C 6 cycloalkyl, or —O—C 3 to C 6 cycloalkyl; or,
wherein in Formula (I), R 3 and R 8 are each C 1 to C 8 perfluoro alkyl and the others of R 1 to R 10 and R 11 to R 12 are hydrogen; or,
wherein in Formula (I), R 3 and R 8 are each —CF 3 , and the others of R 1 to R 10 and R 11 to R 12 are hydrogen,
said process comprising reacting a Nickel (II) compound, selected from NiF 2 , NiCl 2 , NiBr 2 , NiI 2 , Ni(OTf) 2 , Ni(BF 4 ) 2 , Ni(OTs) 2 , Ni(glyme)Cl 2 , Ni(glyme)Br 2 , Ni(diglyme)Cl 2 , Ni(diglyme)Br 2 , Ni(NO 3 ) 2 , Ni(OR 13 ) 2 (where R 13 represents-C(O)—C 1 -C 6 -alkyl which is optionally substituted with one of more halogen), Ni(acetyl acetonate) 2 , Ni(Ac) 2 , or mixtures thereof, with at least three equivalents of the trans-stilbene of Formula (I) in the presence of at least two equivalents of an aluminum alkyl of the Formula Al(R 14 ) 3 , wherein R 14 may be the same or different and is selected from C 1 to C 6 alkyl or C 3 to C 6 cycloalkyl.
3 . Process for preparing an air-stable Ni(R) 3 —complex according to claim 2 wherein the aluminum alkyl of the Formula Al(R 14 ) 3 is selected from Al(CH 3 ) 3 or Al(C 2 H 5 ) 3 .
4 . Method comprising conducting an organic synthesis in a reactor and further comprising introducing to the reactor an air-stable Ni(R) 3 —complex according to claim 1 as catalyst or precatalyst, wherein:
Ni represents Ni(0) and R are the same or different and represents a trans-stilbene of the Formula (I):
wherein in Formula (I), R 3 and R 8 are the same or different and are selected from C 1 to C 8 perfluoro alkyl and the others of R 1 to R 10 are hydrogen, and R 11 to R 12 may be the same or different and are selected from H, C 1 to C 6 alkyl, O—C 1 to C 6 alkyl, C 3 to C 6 cycloalkyl, or —O—C 3 to C 6 cycloalkyl; or,
wherein in Formula (I), R 3 and R 8 are each C 1 to C 8 perfluoro alkyl and the others of R 1 to R 10 and R 11 to R 12 are hydrogen; or,
wherein in Formula (I), R 3 and R 8 are each —CF 3 , and the others of R 1 to R 10 and R 11 to R 12 are hydrogen.