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A Catalytic Application of Co/Zr Heterobimetallic Complexes: Kumada Coupling of Unactivated Alkyl Halides with Alkyl Grignard Reagents
Author(s) -
Zhou Wen,
Napoline Jonathan Wesley,
Thomas Christine M.
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100109
Subject(s) - chemistry , alkyl , halide , catalysis , bromide , medicinal chemistry , reagent , beta hydride elimination , cobalt , tris , polymer chemistry , chloride , photochemistry , organic chemistry , biochemistry
Tris(phosphanylamide) early/late heterobimetallic Zr/Co complexes, ClZr(R′NPR 2 ) 3 CoI [R′ = i Pr, R = Ph ( 1 ), R′ = 2,4,6‐trimethylphenyl, R = i Pr ( 2 ), R′ = R = i Pr ( 3 )], have been utilized as catalysts for the cross‐coupling of alkyl halides with n ‐octylmagnesium bromide. While yields are consistently higher for alkyl bromide substrates, it is found that these unusual heterobimetallic complexes are also active towards more challenging alkyl chloride substrates. This is particularly interesting in light of the fact that monometallic cobalt complexes are inert towards these substrates, suggesting that Zr also plays a role in catalysis. Radical trapping studies suggest that a one‐electron transfer radical oxidative addition pathway is operative.