TY - JOUR
T1 - Theoretical Investigation into Selective Benzene Hydroxylation by Ruthenium-Substituted Keggin-Type Polyoxometalates
AU - Ikeda, Kei
AU - Yoshizawa, Kazunari
AU - Shiota, Yoshihito
N1 - Funding Information:
The computations in this work were primarily performed using the computer facilities at the Research Institute for Information Technology, Kyushu University. This work was supported by a Grant-in-Aid for Japan Society for the Promotion of Science Fellows (Grant JP21J12850), the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT), the MEXT projects of Integrated Research Consortium on Chemical Sciences, Cooperative Research Program of Network Joint Research Center for Materials and Devices, Elements Strategy Initiative to Form Core Research Center, and JST-CREST (Grant JPMJCR15P5) and JST-Mirai (Grant JPMJMI18A2).
Publisher Copyright:
© 2021 American Chemical Society.
PY - 2022/1/10
Y1 - 2022/1/10
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.inorgchem.1c02605
DO - 10.1021/acs.inorgchem.1c02605
M3 - Article
C2 - 34890508
AN - SCOPUS:85121604142
SN - 0020-1669
VL - 61
SP - 10
EP - 14
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 1
ER -