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Updated: Oct 10, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Theoretical Investigation into Selective Benzene Hydroxylation by Ruthenium-Substituted Keggin-Type Polyoxometalates
Kei Ikeda1, Kazunari Yoshizawa1, Yoshihito Shiota1
1Institute for Materials Chemistry and Engineering and Integrated Research Consortium on Chemical Science, Kyushu University, Fukuoka 819-0395, Japan.
Abstract:
Benzene hydroxylation catalyzed by ruthenium-substituted Keggin-type polyoxometalates [RuV(O)XW11O39] (RuOX; X = Al, Ga, Si, Ge, P, As, S; heteroatoms; 3 ≤ n ≤ 6) is investigated using the density functional theory approach. As a possible side reaction, the water oxidation reaction is also considered. We found that the rate-determining step for water oxidation by RuOX requires a higher activation free energy than the benzene hydroxylation reaction, suggesting that all of the RuOX catalysts show high chemoselectivity toward benzene hydroxylation. Additionally, the heteroatom effect in benzene hydroxylation by RuOX is discussed. The replacement of Si by X induces changes in the bond length of μ4O-X, resulting in a change in the activation free energy for benzene hydroxylation by RuOX. Consequentially, RuOS is expected to be the most effective catalyst among the (RuOX) catalysts for the benzene hydroxylation reaction.
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