DFT Analysis of Electronic and Bonding Properties in Face-Bridged inorganic Octahedral Clusters M6L14 .

Several theoretical studies shown that in face-bridged octahedral transition metal clusters M6L14 (M = transition metal; L = π-Donor Ligand) the optimal metallic electron (ME) count is of 24 but for many clusters experimentally synthesized, the ME count can vary from 20 to 24 for early transition metals such as molybdenum, tungsten and rhenium, and from 24 to 48 for late transition metals such as cobalt and palladium without altering the architecture of the octahedral cluster core. Density Functional Theory (DFT) calculations were carried out on the species with 20 to 24 metallic electron count in order to rationalize their electronic structure and to explain the