[Published online Journal of Computer Chemistry, Japan Vol.19, 133-135, by J-STAGE]
<Title:> 計算化学を用いた新規メタン水酸化触媒の提案
<Author(s):> 池田 京, Mahyuddin Muhammad Haris, 塩田 淑仁, 吉澤 一成
<Corresponding author E-Mill:> kazunari(at)ms.ifoc.kyushu-u.ac.jp
<Abstract:> Motivated by a recent study on light-induced solar cell that Iridium-oxo complex over WO3 electrode catalyze water oxidation reaction, we investigated the methane hydroxylation reaction by the same complex. Herein we focused on the closed-shell singlet state reaction due to the no-radical intermediate mechanism although this reaction is energetically unfavored reaction. Using intrinsic bond orbital analysis, we found that the C H bond cleavage reaction proceed via the hydride transfer mechanism. From the view point of orbital interaction between σ orbital (C H bond in methane) and π* orbital (Ir=O bond in Ir complex), we demonstrated that the reactivity of the methane hydroxylation reaction in the closed shell singlet state depends on the energy level of π* orbital.
<Keywords:> DFT calculation, Methane hydroxylation, Iridium-oxo complex, IBO analysis, Orbital interaction
<URL:> https://www.jstage.jst.go.jp/article/jccj/19/4/19_2021-0003/_article/-char/ja/
<Title:> 計算化学を用いた新規メタン水酸化触媒の提案
<Author(s):> 池田 京, Mahyuddin Muhammad Haris, 塩田 淑仁, 吉澤 一成
<Corresponding author E-Mill:> kazunari(at)ms.ifoc.kyushu-u.ac.jp
<Abstract:> Motivated by a recent study on light-induced solar cell that Iridium-oxo complex over WO3 electrode catalyze water oxidation reaction, we investigated the methane hydroxylation reaction by the same complex. Herein we focused on the closed-shell singlet state reaction due to the no-radical intermediate mechanism although this reaction is energetically unfavored reaction. Using intrinsic bond orbital analysis, we found that the C H bond cleavage reaction proceed via the hydride transfer mechanism. From the view point of orbital interaction between σ orbital (C H bond in methane) and π* orbital (Ir=O bond in Ir complex), we demonstrated that the reactivity of the methane hydroxylation reaction in the closed shell singlet state depends on the energy level of π* orbital.
<Keywords:> DFT calculation, Methane hydroxylation, Iridium-oxo complex, IBO analysis, Orbital interaction
<URL:> https://www.jstage.jst.go.jp/article/jccj/19/4/19_2021-0003/_article/-char/ja/
