Molecular properties and electronic structure of phenazine ligand in binuclear molybdenum and manganese metal complexes: A density functional theory study

DFT calculations with full geometry optimization have been performed on the series of hypothetical and characterized binuclear compounds of general formula (L3M)(2)(C12N2H8) (M = Mo and Mn, L-3 = (CO)(3), (PH3)(3) and Cp- and C12N2H8 = phenazine ligand). The various structures with syn and anti configurations have been investigated. The phenazine ligand can bind to the metals involving its C-6 and C4N2 rings through eta(6)-eta(4) and eta(6)-eta(6) coordination modes giving rise to syn and anti structures, respectively, in agreement with the favored 34 electron count with closed-shell and open-shell configurations. This study has shown that the electronic communication between the metal centers depends on their oxidation state and the attached ligands. A more crowded attached ligand imposes an anti configuration despite its electron deficiency. (C) 2013 Elsevier Ltd. All rights reserved.