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Isolation of bridging and terminal coinage metal-nitrene complexes.

Authors
  • Dielmann, Fabian1
  • Andrada, Diego M
  • Frenking, Gernot
  • Bertrand, Guy
  • 1 UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California-San Diego , La Jolla, California 92093-0343, United States. , (United States)
Type
Published Article
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Publication Date
Mar 12, 2014
Volume
136
Issue
10
Pages
3800–3802
Identifiers
DOI: 10.1021/ja5007355
PMID: 24559041
Source
Medline
License
Unknown

Abstract

Transition metal complexes featuring a metal-nitrogen multiple bond have been widely studied due to their implication in dinitrogen fixation and catalytic nitrogen-carbon bond formation. Terminal copper- and silver-nitrene complexes have long been proposed to be the key intermediates in aziridination and amination reactions using azides as the nitrogen source. However, due to their high reactivity, these species have eluded isolation and spectroscopic characterization even at low temperatures. In this paper we report that a stable phosphinonitrene reacts with coinage metal trifluoromethanesulfonates, affording bridging and terminal copper- and silver-nitrene complexes, which are characterized by NMR spectroscopy and single crystal X-ray diffraction analysis.

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