Abstract
Ab initio calculations of the geometry and reactivity of 1,2-ketocarbene C6H4O as an intermediate in organic reactions were performed using the second-order Møller-Plesset (MP2) perturbation theory in the 6-311G* basis set. Only the singlet state of the intermediate was considered. An oxirene-like structure (6) with a six-membered ring and a ketene-like structure (5) with a five-membered ring were localized on the potential energy surface. Attempts to locate a quinone type structure characteristic of aliphatic ketocarbenes failed. The energy of structure5 is −70 kcal mol−1 lower than that of structure6. Harmonic frequencies and intensities of normal vibrations in the IR spectra of6 and5 were calculated. The activation energy of the Wolff rearrangement6→5 was estimated at 12.5 kcal mol−1. The geometry of the transition state of this reaction resembles the quinone-like structure.
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The Pacific Northwest National Laboratories are multiprogram national laboratories operated by the Battelle Memorial Institute.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1663–1667, September, 1999.
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Borisov, Y.A., Garrett, B.C. & Feller, D. Ab initio study of the Wolff rearrangement of C6H4O intermediate in the gas phase. Russ Chem Bull 48, 1642–1646 (1999). https://doi.org/10.1007/BF02494806
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DOI: https://doi.org/10.1007/BF02494806