A mixed-valent high spin(μ-hydroxo)dicobalt(Ⅱ/Ⅲ) complex and its end-on type dioxygen adduct: synthesis, geometric and electronic structure studies  

作　　者：Ceng-Ceng Du Si-Jun Xie Dan-Dan Zhai Zhang-Jie Shi Huayi Fang 

机构地区：[1]Department of Chemistry,Fudan University,Shanghai 200433,China [2]School of Materials Science and Engineering,Tianjin Key Lab for Rare Earth Materials and Applications,Nankai University,Tianjin 300350,China

出　　处：《Science China Chemistry》2021年第10期1693-1697,共5页中国科学（化学英文版）

基　　金：the National Natural Science Foundation of China(21988101,21801044,22071122,U19B6002);Shanghai Sailing Program(18YF1401800)。

摘　　要：A mixed-valent high spin (μ-hydroxo)dicobalt(Ⅱ/Ⅲ) complex bearing N,N′-bis(5-tertbutylsalicylidene)-1,2-diaminobenzene(Salophen^(tBu)) ligand was synthesized by reacting (Salophen^(tBu))Co(Ⅱ)(Py) with O_(2) at low temperature.This complex was isolated and structurally characterized by single crystal X-ray diffraction and infrared spectrum.Magnetic measurement showed a quartet ground state for this complex at room temperature,which was also supported by electron paramagnetic resonance (EPR)characterization.Computational investigations indicated the deviation of the equatorial N_(2)O_(2) coordination geometry around the Co(Ⅱ) center from plane stabilized the quartet state.The end-on type O_(2) adduct of this (μ-hydroxo)dicobalt(Ⅱ/Ⅲ) complex was isolated as dark-brown crystals and structurally and spectroscopically characterized.EPR measurement of this compound in solid state at room temperature presented an isotropic singlet at g~2,revealing the superoxide-like electronic feature of the coordinated O_(2) and was in line with the calculation results.The reactivity of the Co(Ⅲ)-O_(2) complex with N-hydroxyphthalimide,which can act as hydrogen atom donor,was also examined.

关 键 词：dicobalt complex MIXED-VALENT electronic structure dioxygen adduct 

分 类 号：O641.4[理学—物理化学]