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 Hoff

Research output: Contribution to journalArticle

11 Citations (Scopus)

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
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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Molybdenum
Extrusion
Nitrogen
Atoms
Molecules
Nitriles
Kinetics
benzonitrile

ASJC Scopus subject areas

  • Chemistry(all)

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

In: Journal of the American Chemical Society, Vol. 128, No. 14, 12.04.2006, p. 4881-4891.

Research output: Contribution to journalArticle

Mendiratta, Arjun ; Cummins, Christopher C. ; Kryatova, Olga P. ; Rybak-Akimova, Elena V. ; McDonough, James E. ; Hoff, Carl. / 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. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 14. pp. 4881-4891.
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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.",
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AU - Mendiratta, Arjun

AU - Cummins, Christopher C.

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AU - McDonough, James E.

AU - Hoff, Carl

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AB - 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.

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