化学
反应性(心理学)
电子顺磁共振
氧化还原
配体(生物化学)
X射线吸收光谱法
结晶学
分子内力
离解(化学)
电子转移
无机化学
氢氧化物
吸收光谱法
光化学
立体化学
物理化学
核磁共振
物理
病理
受体
医学
量子力学
替代医学
生物化学
作者
Tong Wu,Samantha N. MacMillan,Khashayar Rajabimoghadam,Maxime A. Siegler,Kyle M. Lancaster,Isaac Garcia‐Bosch
摘要
Structural, spectroscopic, and reactivity studies are presented for an electron transfer series of copper hydroxide complexes supported by a tridentate redox-active ligand. Single crystal X-ray crystallography shows that the mononuclear [CuOH]1+ core is stabilized via intramolecular H-bonds between the H-donors of the ligand and the hydroxide anion when the ligand is in its trianionic form. This complex undergoes two reversible oxidation processes that produce two metastable “high-valent” CuOH species, which can be generated by addition of stoichiometric amounts of 1e– oxidants. These CuOH species are characterized by an array of spectroscopic techniques including UV–vis absorption, electron paramagnetic resonance (EPR), and X-ray absorption spectroscopies (XAS), which together indicate that all redox couples are ligand-localized. The reactivity of the complexes in their higher oxidation states toward substrates with modest O–H bond dissociation energies (e.g., 4-substitued-2,6-di-tert-butylphenols) indicates that these complexes act as 2H+/2e– oxidants, differing from the 1H+/1e– reactivity of well-studied [CuOH]2+ systems.
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