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Updated: Apr 27, 2026

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the
Masaaki Yoshifuji1, Shigekazu Ito2
1Department of Chemistry, Graduate School of Science, Tohoku University, Aoba, Sendai 980-8578, Japan.
Abstract:
The intramolecular C-H insertion of the Mes*-substituted phosphanylidenecarbene [Mes*P=C:] (Mes* = 2,4,6-t-Bu3C6H2) and physicochemical properties of the cyclized product, 6,8-di-tert-butyl-3,4-dihydro-4,4-dimethyl-1-phosphanaphthalene were studied based on ab initio calculations. Whereas the alternative Fritsch-Buttenberg-Wiechell-type rearrangement requires almost no activation energy, the intramolecular cyclization needs an activation energy of 12.3 kcal/mol at the MP2(full)/6-31G(d) condition. DFT calculations supported that the optimized structure of the cyclization product of Mes*P=C: suggests remarkable conjugation effects between the nearly coplanar P=C skeleton and the aryl moiety.
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