N−N Bond Forming Reductive Elimination via a Mixed-Valent Nickel(II)–Nickel(III) Intermediate
Justin B. Diccianni
Chemistry Department, New York University, 100 Washington Square E., New York, NY, 10003 USA
Search for more papers by this authorDr. Chunhua Hu
Chemistry Department, New York University, 100 Washington Square E., New York, NY, 10003 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Tianning Diao
Chemistry Department, New York University, 100 Washington Square E., New York, NY, 10003 USA
Search for more papers by this authorJustin B. Diccianni
Chemistry Department, New York University, 100 Washington Square E., New York, NY, 10003 USA
Search for more papers by this authorDr. Chunhua Hu
Chemistry Department, New York University, 100 Washington Square E., New York, NY, 10003 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Tianning Diao
Chemistry Department, New York University, 100 Washington Square E., New York, NY, 10003 USA
Search for more papers by this authorGraphical Abstract
A “paddle-wheel” Ni complex undergoes N−N bond forming reductive elimination under oxidative conditions. The intermediate is a mixed-valent NiII–NiIII complex with a Ni–Ni bond order of zero.
Abstract
Natural products containing N–N bonds exhibit important biological activity. Current methods for constructing N−N bonds have limited scope. An advanced understanding of the fundamental N−N bond formation/cleavage processes occurring at the transition-metal center would facilitate the development of catalytic reactions. Herein we present an N−N bond-forming reductive elimination, which proceeds via a mixed-valent NiII–NiIII intermediate with a Ni–Ni bond order of zero. The discrete NiII–NiIII oxidation states contrast with the cationic dimeric Ni analogue, in which both Ni centers are equivalent with an oxidation state of 2.5. The electronic structures of these mixed-valent complexes have implications for the fundamental understanding of metal–metal bonding interactions.
Supporting Information
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