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.
Keywords: Ligand-Ligand Cooperativity; Non-Innocence Ligands; Noncovalent Interactions; Redox Chemistry.
© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.