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Conformation, hydration, and ligand exchange process of ruthenium nitrosyl complexes in aqueous solution; Free-energy calculations by a combination of molecular-orbital theories and different solvent models

Kido, Kentaro ; Kaneko, Masashi   

Distribution of solvent molecules near transition-metal complex is key information to comprehend the functionality, reactivity and so on. However, polarizable continuum solvent models still are the standard and conventional partner of molecular-orbital (MO) calculations in the solution system including transition-metal complex. In this study, we investigate the conformation, hydration structure and ligand substitution reaction between NO$$_2^-$$ and H$$_2$$O in aqueous solution for [Ru(NO)(OH)(NO$$_2$$)$$_4$$]$$^{2-}$$ (${bf A}$), [Ru(NO)(OH)(NO$$_2$$)$$_3$$(ONO)]$$^{2-}$$ (${bf B}$) and [Ru(NO)(OH)(NO$$_2$$)$$_3$$(H$$_2$$O)]$$^-$$ (${bf C}$) using a combination method of MO theories and a state-of-the-art molecular solvation technique (NI-MC-MOZ-SCF). In the complexes, the treatment is essentially required because except for nitrosyl ligand, a strong hydrogen bond is formed between the ligand and solvent water. These results are complementary to the data previously obtained by $$^{15}$$N NMR experiment. A dominant species is found in the complex ${bf B}$ conformers and, as expected, different between the solvent models, which reveals that molecular solvation beyond continuum media treatment are required for a reliable description of solvation near transition-metal complex. In the stability constant evaluation of ligand substitution reaction, similar to the previous reports, an assumption that considers the direct association between the dissociated nitrite anion and complex ${bf C}$ is useful to obtain a reliable stability constant.



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Category:Chemistry, Multidisciplinary



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