Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Frontier-Orbital Interactions along the Intrinsic Reaction Coordinates of Ketene Dimerizations
Shinichi YamabeTsutomu Minato
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1993 Volume 66 Issue 11 Pages 3283-3288


Ketene dimerizations to diketene and to 1,3-cyclobutanedione are studies theoretically. Their transition state (TS) structures are determined, for the first time, with correlated wavefunctions. The present calculation demonstrates that the two reactions proceed concertedly. The intrinsic reaction coordinates (IRCs) starting from the TSs are traced so as to seek the origin of the selectivity of the two reactions. At their initial stages, a one-center type charge transfer (donative orbital interaction) takes place, enhanced by polarization interactions in the charge-acceptor ketene. The back-donative orbital interactions are found to control the selectivity.

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© 1993 The Chemical Society of Japan
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