Abstract
Context The geometric and electronic structural futures of group-14 hetero-closo-dodecaborates such as monomers [EB11H11]1−, [EB11H11]2− and dimers [(EB11H11)2]2− [E = C, Si, Ge, Sn and Pb] is analyzed using density functional theory (DFT) method. The structural feature such as metrical parameters and binding interactions are theoretically studied. The dispersion correction method has been used to get more insight. The dispersion correction method improves the metrical parameter of group-14 elements towards experimental parameters. The electronic structure of the clusters has been studied using frontier molecular orbital analysis (FMO). It shows the group-14 elements electronic contribution and possible electron delocalization between the cages to stabilize the dimeric clusters. The thermochemistry from numerical frequency analysis suggests the plausible and synthetic viability of the dimeric clusters. The spectroscopic studies (1H, 11B, 13C and 119Sn) elucidate the structures of the cluster with chemical shifts (δ) of lower belt, upper belt and apical boron vertices. The global reactive descriptors and local descriptors are calculated to analyze the philicity of the clusters. According to the descriptor analysis, an identification of reactive sites with respect to an electrophilic and nucleophilic centers of the reactant has been reported.Methods The density functional BP86 with Grimm’s dispersion correction DFT-D3 method has been used to study the bonding interactions of group-14 hetero-closo-dodecaborate dimers. And, the Def2-TZVP basis set applied to this cluster system to investigate electronic structural features using ORCA software (v 5.0.4).