Co6H8(PiPr3)6: A Cobalt Octahedron with Face‐Capping Hydrides |
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| Authors: | Prof. Yasuhiro Ohki Yuki Shimizu Ryoichi Araake Prof. Mizuki Tada Prof. W. M. C. Sameera Prof. Jun‐Ichi Ito Prof. Hisao Nishiyama |
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| Affiliation: | 1. Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Japan;2. PRESTO, Japan, Science and Technology Agency (JST), Kawaguchi, Saitama, Japan;3. Research Center for Materials Science (RCMS) & Integrated Research Consortium on Chemical Sciences (IRCCS), Nagoya University, Japan;4. Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo, Japan;5. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Japan |
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| Abstract: | A square‐planar Co4 amide cluster, Co4{N(SiMe3)2}4 ( 2 ), and an octahedral Co6 hydride cluster, Co6H8(PiPr3)6 ( 4 ), were obtained from metathesis‐type amide to hydride exchange reactions of a CoII amide complex with pinacolborane (HBpin) in the absence/presence of PiPr3. The crystal structure of 4 revealed face‐capping hydrides on each triangular [Co3] face, while the formal CoII2CoI4 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. |
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| Keywords: | clusters cobalt hydride hydrosilylation |
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