Organometallic Nickel(III) Complexes Relevant to Cross-Coupling and Carbon-Heteroatom Bond Formation Reactions

被引:160
|
作者
Zheng, Bo [1 ]
Tang, Fengzhi [1 ]
Luo, Jia [1 ]
Schultz, Jason W. [1 ]
Rath, Nigam P. [2 ]
Mirica, Liviu M. [1 ]
机构
[1] Washington Univ, Dept Chem, St Louis, MO 63130 USA
[2] Univ Missouri, Dept Chem & Biochem, St Louis, MO 63121 USA
基金
美国国家科学基金会;
关键词
COENZYME-M REDUCTASE; TRANSITION-METAL-COMPLEXES; UNACTIVATED ALKYL-HALIDES; ELECTRON-SPIN-RESONANCE; RAY CRYSTAL-STRUCTURE; OXYGEN-ATOM TRANSFER; OXIDATIVE-ADDITION; NITROUS-OXIDE; REACTIVITY; ARYL;
D O I
10.1021/ja5024749
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Nickel complexes have been widely employed as catalysts in C-C and C heteroatom bond formation reactions. In addition to Ni(0) and Ni(II) intermediates, several Ni-catalyzed reactions are proposed to also involve odd-electron Ni(I) and Ni(III) oxidation states. We report herein the isolation, structural and spectroscopic characterization, and organometallic reactivity of Ni(III) complexes containing aryl and alkyl ligands. These Ni(III) species undergo transmetalation and/or reductive elimination reactions to form new C-C or C heteroatom bonds and are also competent catalysts for Kumada and Negishi cross-coupling reactions. Overall, these results provide strong evidence for the direct involvement of organometallic Ni(111) species in cross-coupling reactions and oxidatively induced C-heteroatom bond formation reactions.
引用
收藏
页码:6499 / 6504
页数:6
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