Defining the electronic and geometric structure of one-electron oxidized copper-bis-phenoxide complexes.
Defining the electronic and geometric structure of one-electron oxidized copper-bis-phenoxide complexes.
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DOI：
10.1021/ja804339m
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发表时间：
2008-11-19
影响因子：
15
通讯作者：
Stack, T. Daniel P.
中科院分区：
文献类型：
--
作者：
Storr, Tim;Verma, Pratik;Pratt, Russell C.;Wasinger, Erik C.;Shimazaki, Yuichi;Stack, T. Daniel P.
研究了一个含非无辜salen配体的氧化铜配合物（[CuSal]+; Sal = N，N′-双（3，5-二叔丁基水杨醛）-1，2-环己烷-（1 R，2 R）-二胺）的固态和溶液几何结构和电子结构.整合的信息，从紫外-可见-近红外光谱，磁化率，电化学，共振拉曼光谱，X-射线晶体学，X-射线吸收光谱和密度泛函理论计算提供了重要的见解的性质的本地化/离域的氧化位点。与类似的Ni衍生物[NiSal]+（Storr，T.; Angew等著。化学成分：Int.Ed.2007，46，5198），其仅以Ni（II）配体-自由基形式存在，氧化位点对于[CuSal]+是基于金属的，仅提供固态（4-300 K）的Cu（III）物质。变温溶液研究表明，[CuSal]+存在于配体自由基物种[Cu（II）Sal·]+（S = 1）和高价金属形式[Cu（III）Sal]+（S = 0）之间的可逆自旋平衡中，表明几乎是等能物种。令人惊讶的是，双亚胺-双酚盐连接稳定了Cu（III）的氧化态，并且甚至更令人惊讶的是，在溶液中发生自旋平衡而没有配位数的变化。氧化的四氢salen类似物[CuSalred]+（Salred = N，N′-bis（3，5-di-tert-butylhydroxybenzyl）-1，2-chexanediamine）在溶液中以温度不变的Cu（II）-配体-自由基络合物的形式存在，表明配体结构表面上的简单变化影响了Cu-双酚盐络合物中的氧化位点。
The geometric and electronic structure of an oxidized Cu complex ([CuSal]+; Sal = N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV–vis–NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal]+ (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal]+, affording exclusively a Cu(III) species in the solid state (4–300 K). Variable-temperature solution studies suggest that [CuSal]+ exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal•]+ (S = 1) and the high-valent metal form [Cu(III)Sal]+ (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine–bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSalred]+ (Salred = N, N′-bis(3,5-di-tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)–ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu–bis-phenoxide complexes.
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