Periodic trends and easy estimation of relative stabilities in 11-vertex nido-p-block-heteroboranes and -borates

Abstract

Density functional theory computations were carried out for 11-vertex nido-p-block-hetero(carba)boranes and -borates containing silicon, germanium, tin, arsenic, antimony, sulfur, selenium and tellurium heteroatoms. A set of quantitative values called ''estimated energy penalties'' was derived by comparing the energies of two reference structures that differ with respect to one structural feature only. These energy penalties behave additively, i.e., they allow us to reproduce the DFT-computed relative stabilities of 11-vertex nidoheteroboranes in general with good accuracy and to predict the thermodynamic stabilities of unknown structures easily. Energy penalties for neighboring heteroatoms (HetHet and HetHet¢) decrease down the group and increase along the period (indirectly proportional to covalent radii). Energy penalties for a fiverather than four-coordinate heteroatom, [Het 5k (1) and Het 5k (2)], generally, increase down group 14 but decrease down group 16, while there are mixed trends for group 15 heteroatoms. The sum of HetHet¢ energy penalties results in different but easily predictable openface heteroatom positions in the thermodynamically most stable mixed heterocarbaboranes and -borates with more than two heteroatoms.