Synthesis, Reactivity, and Catalytic Application of a Nickel Pincer Hydride Complex

被引：91

作者：

Breitenfeld, Jan ^{[1
]}

Scopelliti, Rosario ^{[1
]}

Hu, Xile ^{[1
]}

机构：

[1] Ecole Polytech Fed Lausanne, Inst Chem Sci & Engn, Lab Inorgan Synth & Catalysis, SB ISIC, CH-1015 Lausanne, Switzerland

来源：

ORGANOMETALLICS | 2012年 / 31卷 / 06期

基金：

瑞士国家科学基金会;

关键词：

NONACTIVATED ALKYL-HALIDES; CROSS-COUPLING REACTIONS; GRIGNARD-REAGENTS; ELECTRON-TRANSFER; H BONDS; ACTIVATION; LIGANDS; REDUCTION; CHEMISTRY; PALLADIUM;

D O I：

10.1021/om201279j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The nickel(II) hydride complex [((N2N)-N-Me)Ni-H] (2) was synthesized by the reaction of [((N2N)-N-Me)Ni-OMe] (6) with Ph2SiH2 and was characterized by NMR and IR spectroscopy as well as X-ray crystallography. 2 was unstable in solution, and it decomposed via two reaction pathways. The first pathway was intramolecular N-H reductive elimination to give (N2NH)-N-Me and nickel particles. The second pathway was intermolecular, with H-2, nickel particles, and a five-coordinate Ni(II) complex [((N2N)-N-Me)(2)Ni] (8) as the products. 2 reacted with acetone and ethylene, forming [((N2N)-N-Me)Ni-(OPr)-Pr-i] (9) and [((N2N)-N-Me)Ni-Et] (10), respectively. 2 also reacted with alkyl halides, yielding nickel halide complexes and alkanes. The reduction of alkyl halides was rendered catalytically, using [((N2N)-N-Me)Ni-Cl] (1) as catalyst, (NaOPr)-Pr-i or NaOMe as base, and Ph2SiH2 or Me(EtO)(2)SiH as the hydride source. The catalysis appears to operate via a radical mechanism.

引用

页码：2128 / 2136

页数：9

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