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N−N Bond Forming Reductive Elimination via a Mixed‐Valent Nickel(II)–Nickel(III) Intermediate
Author(s) -
Diccianni Justin B.,
Hu Chunhua,
Diao Tianning
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201602566
Subject(s) - nickel , reductive elimination , chemistry , catalysis , cationic polymerization , bond cleavage , metal , transition metal , oxidation state , crystallography , polymer chemistry , organic chemistry
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.