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 lo...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.展开更多
基金the National Natural Science Foundation of China(21988101,21801044,22071122,U19B6002)Shanghai Sailing Program(18YF1401800)。
文摘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.
