Abstract

TORRES, Ana Elizabeth; PANDIYAN, Thangarasu  and  COLMENARES, Fernando. MCSCF-MRMP2 and DFT Exploratory Study on the Stability of Possible Intermediates in the Ru(H₂O)₆²⁺ + H₂O₂ Reaction: Importance of the Multiconfigurational Character in the Description of the Ru=O Moiety. J. Mex. Chem. Soc [online]. 2012, vol.56, n.3, pp.287-293. ISSN 1870-249X.

MCSCF-MRMP2 and DFT calculations were performed in order to analyze the stability and geometrical parameters of some possible intermediates for the reactions Ru²+ + H₂O₂ and Ru(H₂O)₆²⁺ + H₂O₂. At MCSCF-MRMP2 level of calculation, the stability predicted for the Ru^IVO(H₂O)₅²+ suggests an energetic preference of the reaction Ru(H₂O)₆²⁺ + H₂O₂ toward the products involving this high-valence intermediate, in agreement with the commonly accepted mechanism for this kind of reactions. Due to its multiconfigurational character, the DFT approaches used in this work exhibited some limitations for properly describing the RuO^IV(H₂O)₅²+ ion and therefore the energy gap between the possible investigated intermediates.

Keywords : MRMP2; DFT; Ruthenium oxo Compounds; Electron Correlation; Ru^IVO.

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