title: Co6H8(PiPr3)6: A Cobalt Octahedron with Face-Capping Hydrides.
abstract: A square-planar Co4amide cluster, Co4{N(SiMe3)2}4(2), and an octahedral Co6hydride cluster, Co6H8(PiPr3)6(4), were obtained from metathesis-type amide to hydride exchange reactions of a CoIIamide 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 CoII2CoI4oxidation 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.
authors.affiliation: 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.
authors.forename: Yasuhiro
authors.identifier: 0000-0001-5573-2821
authors.initials: Y
authors.lastname: Ohki
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602, Japan.
authors.forename: Yuki
authors.initials: Y
authors.lastname: Shimizu
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602, Japan.
authors.forename: Ryoichi
authors.initials: R
authors.lastname: Araake
authors.affiliation: 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.
authors.forename: Mizuki
authors.initials: M
authors.lastname: Tada
authors.affiliation: Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo, 060-0810, Japan.
authors.forename: W M C
authors.initials: WM
authors.lastname: Sameera
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Japan.
authors.forename: Jun-Ichi
authors.initials: JI
authors.lastname: Ito
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Japan.
authors.forename: Hisao
authors.initials: H
authors.lastname: Nishiyama
keywords: clusters; cobalt; hydride; hydrosilylation