Co6H8(PiPr3)6: A Cobalt Octahedron with Face-Capping Hydrides

被引：21

作者：

Ohki, Yasuhiro ^{[1
,2
]}

Shimizu, Yuki ^{[1
]}

Araake, Ryoichi ^{[1
]}

Tada, Mizuki ^{[1
,3
,4
]}

Sameera, W. M. C. ^{[5
]}

Ito, Jun-Ichi ^{[6
]}

Nishiyama, Hisao ^{[6
]}

机构：

[1] Nagoya Univ, Grad Sch Sci, Dept Chem, Chikusa Ku, Furo Cho, Nagoya, Aichi, Japan

[2] Japan Sci & Technol Agcy JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 3320012, Japan

[3] Nagoya Univ, RCMS, Nagoya, Aichi, Japan

[4] Nagoya Univ, IRCCS, Nagoya, Aichi, Japan

[5] Hokkaido Univ, Dept Chem, Grad Sch Sci, Sapporo, Hokkaido 0600810, Japan

[6] Nagoya Univ, Grad Sch Engn, Dept Appl Chem3, Nagoya, Aichi 4648601, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 51期

基金：

日本科学技术振兴机构;

关键词：

clusters; cobalt; hydride; hydrosilylation; RU CARBONYL CLUSTERS; TETRAHEDRAL MCO3 M; MIXED-METAL; ALPHA; BETA-UNSATURATED KETONES; ASYMMETRIC HYDROSILYLATION; CONJUGATE REDUCTION; NEUTRON-DIFFRACTION; CRYSTAL-STRUCTURES; ARENE LIGANDS; BOND-CLEAVAGE;

D O I：

10.1002/anie.201608262

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A square-planar Co-4 amide cluster, Co-4{N(SiMe3)(2)}(4) (2), and an octahedral Co-6 hydride cluster, Co6H8((PPr3)-Pr-i)(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 (PPr3)-Pr-i. The crystal structure of 4 revealed face-capping hydrides on each triangular [Co-3] face, while the formal (Co2Co4I)-Co-II 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.

引用

页码：15821 / 15825

页数：5

共 55 条

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