Benzonitrile extrusion from molybdenum(IV) ketimide complexes obtained via radical C-E (E = O, S, Se) bond formation: Toward a new nitrogen atom transfer reaction

Arjun Mendiratta, Christopher C. Cummins, Olga P. Kryatova, Elena V. Rybak-Akimova, James E. McDonough, Carl D. Hoff

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11 Scopus citations

Abstract

Beta-elimination is explored as a possible means of nitrogen-atom transfer into organic molecules, Molybdenum(IV) ketimide complexes of formula (Ar[t-Bu]N)3Mo(N=C(X)Ph), where Ar = 3,5-Me2C 6H3 and X = SC6F5, SeC 6F5, or O2CPh, are formally derived from addition of the carbene fragment [:C(X)Ph] to the terminal nitrido molybdenum(VI) complex (Ar[t-Bu]N)3Mo≡N in which the nitrido nitrogen atom is installed by scission of molecular nitrogen. Herein the pivotal (Ar[t-Bu]N)3Mo(N=C(X)Ph) complexes are obtained through independent synthesis, and their propensity to undergo beta-X elimination, i.e., conversion to (Ar[t-Bu]N)3MoX + PhC≡N, is investigated. Radical C-X bond formation reactions ensue when benzonitrile is complexed to the three-coordinate molybdenum(III) complex (Ar[t-Bu]N)3Mo and then treated with 0.5 equiv of X2, leading to facile assembly of the key (Ar[t-Bu]N) 3Mo(N=C(X)Ph) molecules. Treated herein are synthetic, structural, thermochemical, and kinetic aspects of (i) the radical C-X bond formation and (ii) the ensuing beta-X elimination processes. Beta-X elimination is found to be especially facile for X = O2-CPh, and the reaction represents an attractive component of an overall synthetic cycle for incorporation of dinitrogen-derived nitrogen atoms into organic nitrile (R-C≡N) molecules.

Original languageEnglish (US)
Pages (from-to)4881-4891
Number of pages11
JournalJournal of the American Chemical Society
Volume128
Issue number14
DOIs
StatePublished - Apr 12 2006

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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