Co6H8(PiPr3)6: A Cobalt Octahedron with Face-Capping Hydrides
Corresponding Author
Prof. Yasuhiro Ohki
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602 Japan
PRESTO, Japan, Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012 Japan
Search for more papers by this authorYuki Shimizu
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602 Japan
Search for more papers by this authorRyoichi Araake
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602 Japan
Search for more papers by this authorProf. Mizuki Tada
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602 Japan
Research Center for Materials Science (RCMS) & Integrated Research Consortium on Chemical Sciences (IRCCS), Nagoya University, Japan
Search for more papers by this authorProf. W. M. C. Sameera
Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo, 060-0810 Japan
Search for more papers by this authorProf. Jun-Ichi Ito
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Japan
Search for more papers by this authorProf. Hisao Nishiyama
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Japan
Search for more papers by this authorCorresponding Author
Prof. Yasuhiro Ohki
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602 Japan
PRESTO, Japan, Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012 Japan
Search for more papers by this authorYuki Shimizu
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602 Japan
Search for more papers by this authorRyoichi Araake
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602 Japan
Search for more papers by this authorProf. Mizuki Tada
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602 Japan
Research Center for Materials Science (RCMS) & Integrated Research Consortium on Chemical Sciences (IRCCS), Nagoya University, Japan
Search for more papers by this authorProf. W. M. C. Sameera
Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo, 060-0810 Japan
Search for more papers by this authorProf. Jun-Ichi Ito
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Japan
Search for more papers by this authorProf. Hisao Nishiyama
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Japan
Search for more papers by this authorGraphical Abstract
Reactive cobalt clusters: The octahedral Co6–hydride cluster Co6H8(PiPr3)6 and the square-planar Co4 cluster Co4{N(SiMe3)2}4 were synthesized from the reactions of a CoII amide complex with pinacolborane in the presence and absence of PiPr3, respectively. The Co6–hydride cluster catalyzes the conjugate hydrosilylation of 2-cyclohexen-1-one.
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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