Structural control of μ-hydroxo-μ-peroxodicobalt(III) complex with the 6-hpa dinucleating ligand to enhance O2-evolution activity in catalytic water oxidation

Yuki Tanaka; Osamu Iwanaga; Kyosuke Fujikawa; Seina Shinomiya; Hiroaki Kitagishi; Sachiko Yanagisawa; Minoru Kubo; Tetsuya Kambe; Shigenobu Masaoka; Masahito Kodera

doi:10.1039/D5DT01140J

Structural control of μ-hydroxo-μ-peroxodicobalt(iii) complex with the 6-hpa dinucleating ligand to enhance O₂-evolution activity in catalytic water oxidation†

Yuki Tanaka,^a Osamu Iwanaga,^a Kyosuke Fujikawa,^a Seina Shinomiya,^a Hiroaki Kitagishi,

^a Sachiko Yanagisawa,^b Minoru Kubo,^b Tetsuya Kambe,

^c Shigenobu Masaoka

^c and Masahito Kodera

*^a

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* Corresponding authors

^a Department of Molecular Chemistry and Biochemistry, Doshisha University, Kyotanabe, Kyoto 610-0321, Japan
E-mail: mkodera@mail.doshisha.ac.jp

^b Graduate School of Science, University of Hyogo, 3-2-1 Kouto, Kamigori, Ako, Hyogo 678-1297, Japan

^c Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

Abstract

The 6-hpa ligand forms a μ-hydroxo-μ-peroxodicobalt(III) complex [Co(μ-OH)(μ-O₂)(6-hpa)]X₃ (X = ClO₄ (1a) and PF₆ (1b)) and controls the formation of syn configuration. Electrochemical studies revealed that the 6-hpa ligand lowers the oxidation potential of the peroxide moiety by 0.13 V and twice enhances O₂ evolution during catalytic water oxidation by fixing the syn configuration.

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Structural control of μ-hydroxo-μ-peroxodicobalt(iii) complex with the 6-hpa dinucleating ligand to enhance O₂-evolution activity in catalytic water oxidation†

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Structural control of μ-hydroxo-μ-peroxodicobalt(III) complex with the 6-hpa dinucleating ligand to enhance O₂-evolution activity in catalytic water oxidation

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