Fine-Tuning Redox Properties of Heteroleptic Molybdenum Complexes through Ligand-Ligand-Cooperativity |
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| Authors: | Dr Benedict J Elvers Sebastian Pätsch Dr Siva S M Bandaru Prof Dr Vera Krewald Prof Dr Carola Schulzke Dr Christian Fischer |
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| Institution: | 1. Bioinorganic Chemistry, Institute for Biochemistry, University of Greifswald, 17489 Greifswald, Germany;2. Theoretical Chemistry, Institute for Chemistry, TU Darmstadt, 64287 Darmstadt, Germany |
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| Abstract: | Heteroleptic molybdenum complexes bearing 1,5-diaza-3,7-diphosphacyclooctane (P2N2) 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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| Keywords: | Ligand-Ligand Cooperativity Non-Innocence Ligands Noncovalent Interactions Redox Chemistry |
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