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

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, struct...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2014-04, Vol.136 (17), p.6499-6504
Main Authors: Zheng, Bo, Tang, Fengzhi, Luo, Jia, Schultz, Jason W, Rath, Nigam P, Mirica, Liviu M
Format: Article
Language:English
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Summary: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(III) species in cross-coupling reactions and oxidatively induced C–heteroatom bond formation reactions.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja5024749