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Co 6 H 8 (P i Pr 3 ) 6 : A Cobalt Octahedron with Face‐Capping Hydrides
Author(s) -
Ohki Yasuhiro,
Shimizu Yuki,
Araake Ryoichi,
Tada Mizuki,
Sameera W. M. C.,
Ito JunIchi,
Nishiyama Hisao
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201608262
Subject(s) - octahedron , amide , hydrosilylation , hydride , cobalt , chemistry , cluster (spacecraft) , crystallography , metathesis , stereochemistry , crystal structure , medicinal chemistry , catalysis , inorganic chemistry , organic chemistry , metal , polymerization , programming language , computer science , polymer
A square‐planar Co 4 amide cluster, Co 4 {N(SiMe 3 ) 2 } 4 ( 2 ), and an octahedral Co 6 hydride cluster, Co 6 H 8 (P i Pr 3 ) 6 ( 4 ), were obtained from metathesis‐type amide to hydride exchange reactions of a Co II amide complex with pinacolborane (HBpin) in the absence/presence of P i Pr 3 . The crystal structure of 4 revealed face‐capping hydrides on each triangular [Co 3 ] face, while the formal Co II 2 Co I 4 oxidation state of 4 indicated a reduction of the cobalt centers during the assembly process. Cluster 4 catalyzes the hydrosilylation of 2‐cyclohexen‐1‐one favoring the conjugate reduction. Generation of the catalytically reactive Co cluster species was indicated by a trapping experiment with a chiral chelating agent.