Abstract
By sulfurization of phosphaalkenes (a) either (σ^3^,λ^5^)‐phosphoranes (b) or (σ^3^,λ^3^)‐thiaphosphiranes (c) are formed. In this study, Density Functional Theory (DFT) and coupled cluster (CCSD(T)) calculations have been carried out for model and experimental structures of (σ^3^,λ^5^)‐phosphoranes and (σ^3^,λ^3^)‐thiaphosphiranes to elucidate the factors influencing relative stabilities of b and c. According to the results of quantum chemical calculations, sterically bulky substituents make the phosphorane form more favored. Conversely, electronic effects of the most substituents provide higher stability for thiaphosphirane isomers. The only exception has been found in the cases where the substituent at the phosphorus atom possesses π‐donor and σ‐acceptor properties (e.g., in the case of amino group) and the substituents at carbon atom exhibit σ‐donor/π‐acceptor effects (e.g., silyl groups). The stability of the cyclic form c decreases further, if the substituents at the carbon atom are amino groups. In this case, a quite unusual structure has been theoretically predicted, which is considerably different from those of the hitherto known phosphoranes. It indicates a pyramidal configuration at the phosphorus atom and can be conventionally presented as a donor–acceptor adduct of diaminocarbene with thioxophosphine. © 2012 Wiley Periodicals, Inc.