Abstract
A comprehensive theoretical study has been performed for the Schonberg rearrangement of O,O-diphenyl carbonothioate to O,S-diphenyl carbonothioate. The rate constant from the CBS-QB3/Eckart method in diphenyl ether was expressed via two- and three-parameters conventional Arrhenius equations k=1.34×1013exp-21550.4/T and k=1.09×1010T0.997exp-2.1089.7/T respectively. The topological analyses have been performed at the B3LYP/CBSB7 level to unravel the molecular mechanism of the Schonberg rearrangement. The sequence of turning points was 3-C†TSC-0 and can be described by the following: (a) transformation of V(C1,O1) valence basin into two monosynaptic basins V(C1) and V3(O1) accounting for the homolytic breaking of C1 − O1 bond; (b) merging of monosynaptic basins V(C1) and V3(S) into the single disynaptic basin V(C1,S) accounting for the C1- to -S coupling of pseudoradical centers; and formation of new C1 − S bond. The first turning point takes place near the saddle point indicating that activation energy of the Schonberg rearrangement is mainly associated with the breaking of single C O bond.
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