A computational study of the reactivities of four‐membered heavy carbene systems

The potential energy surfaces for the chemical reactions of four‐membered N‐heterocyclic group 14 heavy carbene species have been studied using density functional theory (B3LYP/LANL2DZ). Five four‐membered group 14 heavy carbene species, ( i ‐Pr) 2 NP(NR) 2 E:, in which E = C, Si, Ge, Sn, and Pb, were chosen as the model reactants in this work. Also, four kinds of chemical reactions, CH bond insertion, water addition, alkene cycloaddition, and dimerization, have been used to study the chemical reactivities of these group 14 four‐membered N‐heterocyclic carbene species. Basically, our present theoretical work predicts that the larger the ∠NEN bond angle of the four‐membered group 14 heavy carbene species, the smaller the singlet‐triplet splitting, the lower the activation barrier, and, in turn, the more rapid, its chemical reactions to various chemical species. Moreover, our theoretical investigations suggest that the relative carbenic reactivity decreases in the order: C > Si > Ge > Sn > Pb. That is, the heavier the group 14 atom (E), the more stable is its four‐membered carbene toward chemical reactions. As a result, our results predict that the four‐membered group 14 heavy carbene species (E = Si, Ge, Sn, and Pb) should be more kinetically stable than the observed carbene species and, thus, can be also readily synthesized and isolated at room temperature. Furthermore, the singlet‐triplet energy splitting of the four‐membered group 14 carbene species, as described in the configuration mixing model attributed to the work of Pross and Shaik, can be used as a diagnostic tool to predict their reactivities. The results obtained allow a number of predictions to be made. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011