Influence of hydroxyl substitution on benzyne properties. Quantum chemical characterization of the didehydrophenols

W. T.G. Johnson, C. J. Cramer

Research output: Contribution to journalArticle

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Abstract

Geometries and singlet-triplet splittings for the 10 geometrical isomers of didehydrophenol are characterized at a variety of levels of electronic structure theory. The influence of the hydroxyl group is primarily to increase/decrease the weight of zwitterionic singlet mesomers that place positive/negative charge adjacent to oxygen in valence bond descriptions of the arynes. For some of the meta isomers, this interaction stabilizes distortion in the direction of a bicyclic geometry. The net effect, relative to the unsubstituted benzynes, is to increase the singlet-triplet splittings in 2,3-, 2,6-, and 3,5-didehydrophenol and to decrease that splitting in 2,4- and 2,5-didehydrophenol (3,4-didehydrophenol is essentially unaffected). As shown for other arynes, the singlet-triplet splittings can also be accurately estimated by correlation with proton hyperfine coupling constants in antecedent monoradicals, these values being accessible from very economical calculations.

Original languageEnglish (US)
Pages (from-to)923-928
Number of pages6
JournalJournal of the American Chemical Society
Volume123
Issue number5
DOIs
StatePublished - Feb 7 2001

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