Fine-Tuning Redox Properties of Heteroleptic Molybdenum Complexes through Ligand-Ligand-Cooperativity
Benedict J Elvers1,2, Sebastian Pätsch1, Siva S M Bandaru1
1Bioinorganic Chemistry, Institute for Biochemistry, University of Greifswald, 17489, Greifswald, Germany.
Abstract:
Heteroleptic molybdenum complexes bearing 1,5-diaza-3,7-diphosphacyclooctane (P2 N2 ) and non-innocent dithiolene ligands were synthesized and electrochemically characterized. The reduction potentials of the complexes were found to be fine-tuned by a synergistic effect identified by DFT calculations as ligand-ligand cooperativity via non-covalent interactions. This finding is supported by electrochemical studies combined with UV/Vis spectroscopy and temperature-dependent NMR spectroscopy. The observed behavior is reminiscent of enzymatic redox modulation using second ligand sphere effects.
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