Thermodynamic and Kinetic Study of Cleavage of the N–O Bond of N-Oxides by a Vanadium(III) Complex: Enhanced Oxygen Atom Transfer Reaction Rates for Adducts of Nitrous Oxide and Mesityl Nitrile Oxide

Taryn D. Palluccio, Elena V. Rybak-Akimova, Subhojit Majumdar, Xiaochen Cai, Megan Chui, Manuel Temprado, Jared S Silvia, Anthony Cozzolino, Daniel Tofan, Alexandria Velian, Christopher C Cummins, Burjor Captain, Carl D Hoff

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Abstract

Thermodynamic, kinetic, and computational studies are reported for oxygen atom transfer (OAT) to the complex V(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2, 1) from compounds containing N–O bonds with a range of BDEs spanning nearly 100 kcal mol–1: PhNO (108) > SIPr/MesCNO (75) > PyO (63) > IPr/N2O (62) > MesCNO (53) > N2O (40) > dbabhNO (10) (Mes = mesityl; SIPr = 1,3-bis(diisopropyl)phenylimidazolin-2-ylidene; Py = pyridine; IPr = 1,3-bis(diisopropyl)phenylimidazol-2-ylidene; dbabh = 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene). Stopped flow kinetic studies of the OAT reactions show a range of kinetic behavior influenced by both the mode and strength of coordination of the O donor and its ease of atom transfer. Four categories of kinetic behavior are observed depending upon the magnitudes of the rate constants involved: (I) dinuclear OAT following an overall third order rate law (N2O); (II) formation of stable oxidant-bound complexes followed by OAT in a separate step (PyO and PhNO); (III)
Original languageEnglish
Pages (from-to)11357-11372
JournalJournal of the American Chemical Society
DOIs
StatePublished - Jul 18 2013

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    Palluccio, T. D., Rybak-Akimova, E. V., Majumdar, S., Cai, X., Chui, M., Temprado, M., Silvia, J. S., Cozzolino, A., Tofan, D., Velian, A., Cummins, C. C., Captain, B., & Hoff, C. D. (2013). Thermodynamic and Kinetic Study of Cleavage of the N–O Bond of N-Oxides by a Vanadium(III) Complex: Enhanced Oxygen Atom Transfer Reaction Rates for Adducts of Nitrous Oxide and Mesityl Nitrile Oxide. Journal of the American Chemical Society, 11357-11372. https://doi.org/10.1021/ja405395z