Four-Electron Reduction of Dioxygen on a Metal Surface: Models of Dissociative and Associative Mechanisms in a Homogeneous System,Inorganic Chemistry

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Four-Electron Reduction of Dioxygen on a Metal Surface: Models of Dissociative and Associative Mechanisms in a Homogeneous System
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-11-26 , DOI: 10.1021/acs.inorgchem.0c02936
Hajime Kameo _{1,

2} , Shigeyoshi Sakaki ₃ , Yasuhiro Ohki ₁ , Naoki Uehara ₁ , Takuya Kosukegawa ₁ , Hiroharu Suzuki ₁ , Toshiro Takao ₁

Affiliation

Two different four-electron reductions of dioxygen (O₂) on a metal surface are reproduced in homogeneous systems. The reaction of the highly unsaturated (56-electron) tetraruthenium tetrahydride complex 1 with O₂ readily afforded the bis(μ₃-oxo) complex 3 via a dissociative mechanism that includes large electronic and geometric changes, i.e., a four-electron oxidation of the metal centers and an increase of 8 in the number of valence electrons. In contrast, the tetraruthenium hexahydride complex 2 induces a smooth H-atom transfer to the incorporated O₂ species, and the O–OH bond is cleaved to afford the mono(μ₃-oxo) complex 4 via an associative mechanism. Density functional theory calculations suggest that the higher degree of unsaturation in the tetrahydride system induces a significant interaction between the tetraruthenium core and the O₂ moiety, enabling the large changes required for the dissociative mechanism.

中文翻译：

金属表面上双氧的四电子还原：均质系统中解离和缔合机理的模型

在均相系统中会复制金属表面上的两个不同的双氧（O ₂）四电子还原反应。高度不饱和的（56-电子）的反应tetraruthenium复杂四氢化1为O ₂容易得到双（μ ₃ -氧代）络合物3经由包括大型电子和几何变化，即，一个四电子氧化解离机构金属中心和价电子数增加了8。与此相反，六氢化tetraruthenium复杂2诱导的平滑H-原子转移到PJ内置Ò ₂种，和O-OH键断裂，得到单（μ ₃ -氧代）络合物4通过关联机制。密度泛函理论计算表明，四氢化物系统中较高的不饱和度会引起四钌核与O ₂部分之间的显着相互作用，从而使离解机理所需的变化较大。

更新日期：2021-02-01

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