Reactions of organic nitriles with a three-coordinate molybdenum(III) complex and with a related molybdaziridine-hydride
Tsai YC, Stephens FH, Meyer K, Mendiratta A, Gheorghiu MD, Cummins CC (2003)
Publication Type: Journal article, Original article
Publication year: 2003
Journal
Original Authors: Tsai Y.-C., Stephens F.H., Meyer K., Mendiratta A., Gheorghiu M.D., Cummins C.C.
Publisher: American Chemical Society
Book Volume: 22
Pages Range: 2902-2913
Journal Issue: 14
DOI: 10.1021/om030124v
Abstract
Reactions of nitriles RCN with the sterically encumbered Mo(N[t-Bu]Ar) (1, Ar = 3,5-CHMe) or the somewhat less hindered Mo(H)(η-Me CNAr)(N[i-Pr]Ar) (2) have been investigated. Where R = Me or Ph, reaction with 1 results in reductive nitrile coupling and the formation of a diiminato product [u-NC(R)C(R)N][1]. In contrast, reaction of 1 with MeNCN surprisingly results in a stable, albeit highly congested, η adduct of the nitrile. When the less sterically hindered 2 is used, reaction with PhCN gives the diiminato product analogous to the one mentioned for the tert-butyl system, [u-NC(Ph)C(Ph)N] [Mo(N[i-Pr]Ar)], where molybdaziridine-hydride 2 has provided access to the three-coordinate Mo(N[i-Pr]Ar) (3) moiety. Use of a more bulky nitrile such as MesCN (Mes = 2,4,6-CH Me) results in formation of a bis-η compound, (η-MesCN)[3], Use of 9-anthracenylcarbonitrile results in head-to-tail C-C coupling of two monomers via the anthracenyl moiety. Detailed variable-temperature EPR and H NMR data are included for both molybdenum-containing starting materials and selected reaction intermediates and products. © 2003 American Chemical Society.
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APA:
Tsai, Y.-C., Stephens, F.H., Meyer, K., Mendiratta, A., Gheorghiu, M.D., & Cummins, C.C. (2003). Reactions of organic nitriles with a three-coordinate molybdenum(III) complex and with a related molybdaziridine-hydride. Organometallics, 22(14), 2902-2913. https://doi.org/10.1021/om030124v
MLA:
Tsai, Yi-Chou, et al. "Reactions of organic nitriles with a three-coordinate molybdenum(III) complex and with a related molybdaziridine-hydride." Organometallics 22.14 (2003): 2902-2913.
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