Ring Strain Energies of Three-Membered Homoatomic Inorganic Rings El3 and Diheterotetreliranes El2Tt (Tt = C, Si, Ge): Accurate versus Additive Approaches.

Abstract

Accurate ring strain energies (RSEs) for three-membered symmetric inorganic rings El3 and organic dihetero-monocycles El2C and their silicon El2Si and germanium El2Ge analogues have been computed for group 14–16 “El” heteroatoms using appropriate homodesmotic reactions and calculated at the DLPNO-CCSD-(T)/def2-TZVPP//B3LYP-D4/def2-TZVP(ecp) level. Rings containing triels and Sn/Pb heteroatoms are studied as exceptions to the RSE calculation as they either do not constitute genuine rings or cannot use the general homodesmotic reaction scheme due to uncompensated interactions. Some remarkable concepts already related to the RSE such as aromaticity or strain relaxation by increasing the s-character in the lone pair (LP) of the group 15–16 elements are analyzed extensively. An appealing alternative procedure for the rapid estimation of RSEs using additive rules, based on contributions of ring atoms or endocyclic bonds, is disclosed.