Ring Strain Energy of Diheteropnictogeniranes El2Pn (Pn = N, P, As, Sb)- Accurate versus Additive Approaches.

Abstract

Accurate ring strain energy (RSE) values for sixty-six parent pnictogeniranes having two other identical p-block elements, El2Pn, have been reported. A decrease in RSE was observed to correlate with an increase in the p character of the AO used in endocyclic bonds, which is particularly remarkable on descending the groups 15 and 16. The latter also parallels higher -NICS(1) values, which seems not to be related with an increase in aromaticity, as pointed out by other NICS-related criteria, but to atom-centred diatropic currents mostly arising from the presence of lone pairs. Only in case of pnictogenaditrieliranes Tr2Pn (Tr = B, Al, Ga), the decrease of -NICS(1) is related to a lower Hückel-type 2π-electron aromaticity on descending group 13. The use of an additive methodology based on atom-strain contributions enables estimation of a large majority of all possible three-membered rings containing group 13-16 elements with modest accuracy (RMSE = 4.371 kcal/mol), that could be remarkably improved by using bond-strain contributions (RMSE = 1.183 kcal/mol).