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Theoretical modeling of electrochemical interactions in bimetallic molybdenum nitrosyl complexes incorporating saturated bridges |
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| Authors: | Klemens Noga Piotr P. Romańczyk Andrzej J. Włodarczyk Ewa Broclawik |
| Affiliation: | 1. Department of Theoretical Chemistry, Jagiellonian University, Ingardena Street 3, 30-060 Cracow, Poland;2. Faculty of Chemical Engineering and Technology, Cracow University of Technology, Warszawska Street 24, 31-155 Cracow, Poland;3. Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek Street 8, 30-239 Cracow, Poland |
| Abstract: | Hybrid B3LYP and non-hybrid OLYP DFT formalism has been applied to neutral and reduced forms of bimetallic hydrotris(3-methylpyrazol-1-yl)borato (Tp3-Me) molybdenum nitrosyl complexes incorporating ethane-1,2-diolate bridges. Direct evidence for localization of an extra electron in mixed-valence compounds {16e:17e}− is based on the analysis of electron density, energetic stabilization of asymmetric structures with an electron trapped on one Mo and the splitting of both calculated and experimental νNO stretching frequencies. Differences in the first and second electron affinities calculated in PCM solvent model have been successfully related to cyclic voltammetry measurements. Electronic interactions through saturated ethanediolato bridges are evidenced by the extent of spin density delocalization towards the second Mo center. |
| Keywords: | Molybdenum nitrosyl binuclear complex Tris(pyrazolyl)borato ligand Electrochemical interactions Mixed-valence systems DFT modeling |
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