Four-Electron Reduction of Dioxygen on a Metal Surface: Models of Dissociative and Associative Mechanisms in a Homogeneous SystemClick to copy article linkArticle link copied!
- Hajime Kameo*Hajime Kameo*Email: [email protected]Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama 2-12-1, Meguro-ku, Tokyo152-8552, JapanDepartment of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho 1-1, Naka-ku, Sakai, Osaka 599-8531, JapanMore by Hajime Kameo
- Shigeyoshi SakakiShigeyoshi SakakiFukui Institute for Fundamental Chemistry, Kyoto University, Takano-nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103, JapanMore by Shigeyoshi Sakaki
- Yasuhiro OhkiYasuhiro OhkiDepartment of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama 2-12-1, Meguro-ku, Tokyo152-8552, JapanMore by Yasuhiro Ohki
- Naoki UeharaNaoki UeharaDepartment of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama 2-12-1, Meguro-ku, Tokyo152-8552, JapanMore by Naoki Uehara
- Takuya KosukegawaTakuya KosukegawaDepartment of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama 2-12-1, Meguro-ku, Tokyo152-8552, JapanMore by Takuya Kosukegawa
- Hiroharu SuzukiHiroharu SuzukiDepartment of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama 2-12-1, Meguro-ku, Tokyo152-8552, JapanMore by Hiroharu Suzuki
- Toshiro Takao*Toshiro Takao*Email: [email protected]Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama 2-12-1, Meguro-ku, Tokyo152-8552, JapanMore by Toshiro Takao
Abstract
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.
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