Theoretical Investigation into Selective Benzene Hydroxylation by Ruthenium-Substituted Keggin-Type Polyoxometalates

Kei Ikeda, Kazunari Yoshizawa, Yoshihito Shiota

Research output: Contribution to journalArticlepeer-review

Abstract

Benzene hydroxylation catalyzed by ruthenium-substituted Keggin-type polyoxometalates [RuV(O)XW11O39]n- (RuVOX; 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 RuVOX requires a higher activation free energy than the benzene hydroxylation reaction, suggesting that all of the RuVOX catalysts show high chemoselectivity toward benzene hydroxylation. Additionally, the heteroatom effect in benzene hydroxylation by RuVOX 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 RuVOX. Consequentially, RuVOS is expected to be the most effective catalyst among the (RuVOX) catalysts for the benzene hydroxylation reaction.

Original languageEnglish
JournalInorganic chemistry
DOIs
Publication statusAccepted/In press - 2021

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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