Ruthenium(III) acetylacetonate; a homogeneous catalyst in the hydrolysis of sodium borohydride

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2006

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Keçeli, Ezgi

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Ruthenium(III) acetylacetonate was employed for the first time as homogeneous catalyst in the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was not reduced by sodium borohydride under the experimental conditions and remains unchanged after the catalysis, as shown by FT-IR and UV-Vis spectroscopic characterization. Poisoning experiments with mercury, carbon disulfide or trimethylphosphite provide compelling evidence that ruthenium(III) acetylacetonate is indeed a homogenous catalyst in the hydrolysis of sodium borohydride. Kinetics of the ruthenium(III) acetylacetonate catalyzed hydrolysis of sodium borohydride was studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first order with respect to both the substrate concentration and catalyst concentration. The activation parameters of this reaction were also determined from the evaluation of the kinetic data: activation energy; Ea = 25.6 ??1.3 kJ.mol-1, the enthalpy of activation; ?H# = 24.6 ± 1.2 kJ.mol-1 and the entropy of activation ?S# = -170 ± 5 J?mol-1?K-1. Ruthenium(III) acetylacetonate provides the lowest activation energy ever found for the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was found to be highly active catalyst providing 1183 total turnovers in the hydrolysis of sodium borohydride over 180 min before they are deactivated. The recorded turnover frequency (TOF) is 6.55 min-1.

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Inorganic Chemistry.

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http://etd.lib.metu.edu.tr/upload/3/12607230/index.pdf
https://hdl.handle.net/11511/15880

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Graduate School of Natural and Applied Sciences, Thesis

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Citation Formats

E. Keçeli, “Ruthenium(III) acetylacetonate; a homogeneous catalyst in the hydrolysis of sodium borohydride,” M.S. - Master of Science, Middle East Technical University, 2006.