title: N-N Bond Forming Reductive Elimination via a Mixed-Valent Nickel(II)-Nickel(III) Intermediate.
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 Ni(II) -Ni(III) intermediate with a Ni-Ni bond order of zero. The discrete Ni(II) -Ni(III) 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.
authors.affiliation: Chemistry Department, New York University, 100 Washington Square E., New York, NY, 10003, USA.
authors.forename: Justin B
authors.initials: JB
authors.lastname: Diccianni
authors.affiliation: Chemistry Department, New York University, 100 Washington Square E., New York, NY, 10003, USA.
authors.forename: Chunhua
authors.initials: C
authors.lastname: Hu
authors.affiliation: Chemistry Department, New York University, 100 Washington Square E., New York, NY, 10003, USA. diao@nyu.edu.
authors.forename: Tianning
authors.initials: T
authors.lastname: Diao
keywords: N−N bond formation; metal-metal bonding; mixed-valent compounds; nickel; reductive elimination