Olefin epoxidation by dioxiranes and percarboxylic acids: an analysis of activation energies calculated by a density functional method | Zendy

Gisdakis Philip | Zendy; Rösch Notker | Zendy

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Olefin epoxidation by dioxiranes and percarboxylic acids: an analysis of activation energies calculated by a density functional method

Author(s) -

Gisdakis Philip,

Rösch Notker

Publication year - 2001

Publication title -

journal of physical organic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.325

H-Index - 66

eISSN - 1099-1395

pISSN - 0894-3230

DOI - 10.1002/poc.386

Subject(s) - chemistry , dioxirane , olefin fiber , hydrogen peroxide , hydrogen fluoride , homo/lumo , molecular orbital , density functional theory , medicinal chemistry , activation energy , atomic orbital , computational chemistry , proton , organic chemistry , catalysis , molecule , physics , quantum mechanics , electron

The activity of dioxiranes, R 2 CO 2 , and percarboxylic acids, RCO(O 2 )H, in olefin epoxidation reactions can be rationalized by a frontier orbital interaction. Barrier heights of these oxygen transfer reactions, as calculated by a density functional method, depend linearly on the energy of the olefin HOMO orbital π (C—C) and of the peroxide LUMO orbital σ*(O—O). Activation barriers can be predicted from linear relationships with the proton affinity of a dioxirane (as measured by the hydrogen fluoride association energy) or the p K a value of a percarboxylic acid. Copyright © 2001 John Wiley & Sons, Ltd.

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