Coordination diversity of the phenazine ligand in binuclear transition metal sandwich complexes: Theoretical investigation

DFT calculations with full geometry optimization have been carried out for all the low-energy isomers of [M(C12N2H8)](2) (M = Sc-Ni and C12N2H8 = phenazine ligand = Phz). Depending on the metal atoms, phenazine adopts various hapticities that involve full or partial coordination of the C-6 and C4N2 rings. Phenazine is also shown to be quite flexible with respect to the spin ground state. The phenazine ligand can be bound to the metals involving its C-6 and C4N2 rings or its outer C-6 ones through various coordination modes such as eta(4)-eta(4), eta(6)-eta(4) and eta(6)-eta(6), giving rise to the conformations of types (a) and (b). This study has shown that the electronic communication between the metal centers depends on their oxidation state in harmony with the neutral, monoanionic and dianionic phenazine forms. The major structures showed the preference of the coordination in separate way of the metal centers apart from the Ti, V and Co ones. The MO plots, WBIs (Weber bond indices) obtained from the Weinhold nature bond order analysis and the metal-metal bond lengths gave a deeper insight on the metal-metal bonding. Energy decomposition analysis showed that the interactions in the studied compounds are governed by half covalent and half electrostatic character. (C) 2014 Elsevier B. V. All rights reserved.