Facile Transformations of a Binuclear Cp*Co(II) Diamidonaphthalene Complex to Mixed-Valent Co(II)Co(III), Co(III)(μ-H)Co(III), and Co(III)(μ-OH)Co(III) Derivatives

Yufang Xie; Qiyi Miao; Wenhao Deng; Yilei Lu; Yinuo Yang; Xiaohui Chen; Rong-Zhen Liao; Shengfa Ye; Chen-Ho Tung; Wenguang Wang

doi:10.1021/acs.inorgchem.1c03451

Facile Transformations of a Binuclear Cp*Co(II) Diamidonaphthalene Complex to Mixed-Valent Co(II)Co(III), Co(III)(μ-H)Co(III), and Co(III)(μ-OH)Co(III) Derivatives

Inorg Chem. 2022 Jan 31;61(4):2204-2210. doi: 10.1021/acs.inorgchem.1c03451. Epub 2022 Jan 20.

Authors

Yufang Xie¹, Qiyi Miao², Wenhao Deng³, Yilei Lu¹, Yinuo Yang¹, Xiaohui Chen¹, Rong-Zhen Liao³, Shengfa Ye², Chen-Ho Tung¹, Wenguang Wang^{1

4}

Affiliations

¹ School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
² State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
³ School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
⁴ College of Chemistry, Beijing Normal University, Beijing 100875, China.

PMID: 35049285
DOI: 10.1021/acs.inorgchem.1c03451

Abstract

A diamido-bridged dicobalt complex supported by a diamidonaphthalene ligand, Cp*₂Co₂(μ-1,8-C₁₀H₈(NH)₂) (1), was synthesized, and the reactivity relevant to redox transformations of the Co₂N₂ core was investigated. It was found that the Co(II)-Co(II) bond allows for protonation by [HPPh₃][BF₄] resulting in a bridging hydride, [1H]⁺, with pK_a ∼ 7.6 in CH₂Cl₂. The diamidonaphthalene ligand can stabilize the binuclear system in the Co(II)Co(III) mixed-valent state (1⁺), which is capable of binding CO to afford [1-CO]⁺. Surprisingly, the mixed-valent complex also activates H₂O to furnish a Co(III)Co(III) hydroxy complex [1-OH]⁺ accompanied by release of H₂. The hydroxy ligand in [1-OH]⁺ is exchangeable, as demonstrated by ¹⁸O-labeling experiments on [1-OH]⁺ with H₂¹⁸O that led to the heavier isotopolog [1-¹⁸OH]⁺.