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Dihydrogen bond intermediated alcoholysis of dimethylamine-borane in nonaqueous media.
Golub, Igor E; Gulyaeva, Ekaterina S; Filippov, Oleg A; Dyadchenko, Victor P; Belkova, Natalia V; Epstein, Lina M; Arkhipov, Dmitry E; Shubina, Elena S.
Afiliación
  • Golub IE; †A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova 28, 119991 Moscow, Russia.
  • Gulyaeva ES; ‡Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, 119234 Moscow, Russia.
  • Filippov OA; †A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova 28, 119991 Moscow, Russia.
  • Dyadchenko VP; ‡Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, 119234 Moscow, Russia.
  • Belkova NV; †A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova 28, 119991 Moscow, Russia.
  • Epstein LM; ‡Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, 119234 Moscow, Russia.
  • Arkhipov DE; †A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova 28, 119991 Moscow, Russia.
  • Shubina ES; †A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova 28, 119991 Moscow, Russia.
J Phys Chem A ; 119(16): 3853-68, 2015 Apr 23.
Article en En | MEDLINE | ID: mdl-25822484
Dimethylamine-borane (DMAB) acid/base properties, its dihydrogen-bonded (DHB) complexes and proton transfer reaction in nonaqueous media were investigated both experimentally (IR, UV/vis, NMR, and X-ray) and theoretically (DFT, NBO, QTAIM, and NCI). The effects of DMAB concentration, solvents polarity and temperature on the degree of DMAB self-association are shown and the enthalpy of association is determined experimentally for the first time (-ΔH°assoc = 1.5-2.3 kcal/mol). The first case of "improper" (blue-shifting) NH···F hydrogen bonds was observed in fluorobenzene and perfluorobenzene solutions. It was shown that hydrogen-bonded complexes are the intermediates of proton transfer from alcohols and phenols to DMAB. The reaction mechanism was examined computationally taking into account the coordinating properties of the reaction media. The values of the rate constants of proton transfer from HFIP to DMAB in acetone were determined experimentally [(7.9 ± 0.1) × 10(-4) to (1.6 ± 0.1) × 10(-3) mol(-1)·s(-1)] at 270-310 K. Computed activation barrier of this reaction ΔG(‡theor)298 K(acetone) = 23.8 kcal/mol is in good agreement with the experimental value of the activation free energy ΔG(‡exp)270 K = 21.1 kcal/mol.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem A Asunto de la revista: QUIMICA Año: 2015 Tipo del documento: Article País de afiliación: Rusia Pais de publicación: Estados Unidos
Texto completo
Añadir a Mi BVS
Imprimir
XML
PubMed Links
Buscar en Google

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem A Asunto de la revista: QUIMICA Año: 2015 Tipo del documento: Article País de afiliación: Rusia Pais de publicación: Estados Unidos