Coordination diversity of the phenazine ligand in binuclear transition metal sandwich complexes
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Date
2014
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Publisher
Elsevier
Abstract
DFT calculations with full geometry optimization have been carried out for all the low-energy isomers of
[M(C12N2H8)]2 (M ¼ SceNi and C12N2H8 ¼ phenazine ligand ¼ Phz). Depending on the metal atoms,
phenazine adopts various hapticities that involve full or partial coordination of the C6 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 C6 and C4N2 rings or its outer C6 ones through various coordination
modes such as h4eh4, h6eh4 and h6eh6, 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 metalemetal bond lengths gave a deeper insight on the metalemetal bonding.
Energy decomposition analysis showed that the interactions in the studied compounds are governed by
half covalent and half electrostatic character