Organometallic Nickel(III) Complexes Relevant to Cross-Coupling and Carbon–Heteroatom Bond Formation Reactions
- 16 April 2014
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 136 (17), 6499-6504
- https://doi.org/10.1021/ja5024749
Abstract
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.Keywords
Funding Information
- National Science Foundation (CHE- 1255424)
This publication has 69 references indexed in Scilit:
- Pd‐, Ni‐, Fe‐, and Co‐Catalyzed Cross‐Couplings Using Functionalized Zn‐, Mg‐, Fe‐, and In‐OrganometallicsIsrael Journal of Chemistry, 2010
- Secondary Alkyl Halides in Transition‐Metal‐Catalyzed Cross‐Coupling ReactionsAngewandte Chemie-International Edition, 2009
- Nickel-catalysed Negishi cross-coupling reactions: scope and mechanismsChemical Society Reviews, 2009
- Catalysts for Cross‐Coupling Reactions with Non‐activated Alkyl HalidesAngewandte Chemie-International Edition, 2005
- Nickel‐Catalyzed Cross‐Couplings of Unactivated Alkyl Halides and Pseudohalides with Organometallic CompoundsAdvanced Synthesis & Catalysis, 2004
- Metal‐Catalyzed Cross‐Coupling ReactionsPublished by Wiley ,2004
- Suzuki Cross-Couplings of Unactivated Secondary Alkyl Bromides and IodidesJournal of the American Chemical Society, 2004
- Rates and mechanism of biphenyl synthesis catalyzed by electrogenerated coordinatively unsaturated nickel complexesOrganometallics, 1988
- Mechanism of biaryl synthesis with nickel complexesJournal of the American Chemical Society, 1979
- Reductive coupling of organometals induced by oxidation. Detection of metastable paramagnetic intermediatesJournal of the American Chemical Society, 1978