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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structural, electronic, and theoretical description of a series of cobalt clathrochelate complexes in the Co(III), Co(II) and Co(I) oxidation states
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Structural, electronic, and theoretical description of a series of cobalt clathrochelate complexes in the Co(III), Co(II) and Co(I) oxidation states

机译：在Co（III），Co（II）和Co（I）氧化态下一系列钴螯合物的配合物的结构，电子和理论描述

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摘要

Encaged hexacoordinated metal complexes have long been a fascinating family of complexes, as they confer the same ligand environment to metal ions in different oxidation states. We recently reported that cobalt clathrochelate complexes behave as hydrogen-producing catalysts at quite modest overpotential (Pantani et al. Angew. Chem., Int. Ed. 2008, 47, 9948). The electrochemical properties evidenced two quasireversible one-electron reduction waves starting from the cobalt(III) derivative, indicating that there are no dramatic changes in the coordination sphere. The intriguing question is the mechanistic pathways for this observed reactivity. In this work, we compare our observed electrochemical and spectroscopic data (UV-visible and EPR spectroscopies) with our theoretical findings based on DFT, TD-DFT, and CASSCF calculations. The properties of the Co(III) and Co(II) species can be explained as low-spin complexes. In contrast, the doubly reduced species, the "Co(I)" form, is a high-spin complex and its electronic description involves partial reduction of the ligand cage. This point is of major importance to understand the catalytic activity.
机译：包封的六配位金属络合物长期以来一直是一个引人入胜的络合物家族，因为它们为不同氧化态的金属离子赋予相同的配体环境。我们最近报道了笼形螯合钴配合物在相当适度的超电势下起产氢催化剂的作用（Pantani et al.Angew.Chem。，Int.Ed.2008，47，9948）。电化学性质表明，从钴（III）衍生物开始出现了两个准可逆的单电子还原波，表明配位域没有明显变化。有趣的问题是这种观察到的反应性的机制途径。在这项工作中，我们将观察到的电化学和光谱数据（紫外可见和EPR光谱）与基于DFT，TD-DFT和CASSCF计算的理论结果进行了比较。 Co（III）和Co（II）的性质可以解释为低自旋络合物。相反，双还原的物种“ Co（I）”形式是高自旋复合物，其电子描述涉及配体笼的部分还原。这一点对于理解催化活性至关重要。

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