Two-step binding of O 2 to a vanadium(III) trisanilide complex to form a non-vanadyl vanadium(V) peroxo complex

Anthony F. Cozzolino, Daniel Tofan, Christopher C. Cummins, Manuel Temprado, Taryn D. Palluccio, Elena V. Rybak-Akimova, Subhojit Majumdar, Xiaochen Cai, Burjor Captain, Carl D. Hoff

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17 Scopus citations

Abstract

Treatment of V(N[ tBu]Ar) 3 (1) (Ar = 3,5-Me 2C 6H 3) with O 2 was shown by stopped-flow kinetic studies to result in the rapid formation of (η 1-O 2)V(N[ tBu]Ar) 3 (2) (δH = 3.3 ± 0.2 kcal/mol and δS = -22 ± 1 cal mol -1 K -1), which subsequently isomerizes to (η 2-O 2)V(N[ tBu]Ar) 3 (3) (δH = 10.3 ± 0.9 kcal/mol and δS = -6 ± 4 cal mol -1 K -1). The enthalpy of binding of O 2 to form 3 is -75.0 ± 2.0 kcal/mol, as measured by solution calorimetry. The reaction of 3 and 1 to form 2 equiv of O≡V(N[ tBu]Ar) 3 (4) occurs by initial isomerization of 3 to 2. The results of computational studies of this rearrangement (δH = 4.2 kcal/mol; δH = 16 kcal/mol) are in accord with experimental data (δH = 4 ± 3 kcal/mol; δH = 14 ± 3 kcal/mol). With the aim of suppressing the formation of 4, the reaction of O 2 with 1 in the presence of tBuCN was studied. At -45 °C, the principal products of this reaction are 3 and tBuC(=O) N≡V(N[ tBu]Ar) 3 (5), in which the bound nitrile has been oxidized. Crystal structures of 3 and 5 are reported.

Original languageEnglish (US)
Pages (from-to)18249-18252
Number of pages4
JournalJournal of the American Chemical Society
Volume134
Issue number44
DOIs
StatePublished - Nov 7 2012

ASJC Scopus subject areas

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

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    Cozzolino, A. F., Tofan, D., Cummins, C. C., Temprado, M., Palluccio, T. D., Rybak-Akimova, E. V., Majumdar, S., Cai, X., Captain, B., & Hoff, C. D. (2012). Two-step binding of O 2 to a vanadium(III) trisanilide complex to form a non-vanadyl vanadium(V) peroxo complex. Journal of the American Chemical Society, 134(44), 18249-18252. https://doi.org/10.1021/ja309621h