An approach to quantum chemical consideration of "hydride" transfer reactions

An approach to the quantum chemical study of "hydride ion" transfer has been proposed, according to which the sequences of changes in ionization potentials, enthalpies and free energies of the affinities to the hydride ion, to the hydrogen atom and to the proton of substrates molecules and...

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Bibliographic Details
Published in:Journal of the Serbian Chemical Society 2004-01, Vol.69 (6), p.431-439
Main Authors: BORIS I. DREVKO, ALEXEI N. PANKRATOV
Format: Article
Language:English
Subjects:
"hydride" transfer
chalcogenopyrans
quantum chemical consideration
reaction mechanisms
theory experiment correlation
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Summary:An approach to the quantum chemical study of "hydride ion" transfer has been proposed, according to which the sequences of changes in ionization potentials, enthalpies and free energies of the affinities to the hydride ion, to the hydrogen atom and to the proton of substrates molecules and their derivatives (cations, radicals, anions), are compared with the experimentally substantiated series of "hydride" mobility. It has been established that the experimental series of "hydride" mobility for six chalcogenopyrans based on "semicyclic" 1,5-diketones is in conformity with the computed ionization potentials of the molecules, and with the affinity of the corresponding radicals to the hydrogen atom involved in the transfer. The direct splitting-out of the hydride ion and the primary deprotonation of the substrates followed by the withdrawal of two electrons was elucidated to be unlikely. Feasible are the mechanisms of "hydride" mobility, the first step of which consists of electron or hydrogen atom transfer from the chalcogenopyrans molecules.
ISSN:0352-5139
DOI:10.2298/JSC0406431P