Metal‐ versus ligand‐centered redox processes and the effects of substituents on the ligands on the spectroscopic properties of the metal complexes are at the heart of research on metal complexes with non‐innocent ligands. This work presents three examples of chromium complexes that contain both oxido and corrolato ligands, with the substituents on the corrolato ligands being different in the three cases. Combined X‐ray crystallographic, electrochemical, UV/Vis/NIR/EPR spectroelectrochemical, and EXAFS/XANES measurements, together with DFT calculations, have been used to probe the complexes in three different redox forms. This combined approach makes it possible to address questions related to chromium‐ versus corrolato‐centered redox processes, and the accessibility (or not) of Cr^IV, Cr^V, and Cr^VI in these complexes, as well as their spin states. To the best of our knowledge, these are the first EXAFS/XANES investigations on Cr‐corrolato complexes in different redox forms, and hence these data should set benchmarks for future investigations on such complexes by this method.

中文翻译：

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具有氧化基和Corrolato配体的铬配合物：基于金属的氧化还原过程与无配体的纯真

金属相对于配体为中心的氧化还原过程以及取代基对配体的影响对金属配合物的光谱性质的影响是具有非纯配体的金属配合物研究的核心。这项工作提出了同时含有氧化配体和彩晶配体的铬配合物的三个例子，在三种情况下，彩晶配体上的取代基是不同的。结合X射线晶体学，电化学，UV / Vis / NIR / EPR光谱电化学和EXAFS / XANES测量，以及DFT计算，已用于探测三种不同氧化还原形式的配合物。这种结合的方法可以解决与以铬为中心的相对于以Corrolato为中心的氧化还原过程有关的问题，以及Cr ^IV，Cr ^V的可及性（或不可及），以及这些络合物中的Cr ^VI以及它们的自旋态。据我们所知，这是对不同氧化还原形式的Cr-corrolato配合物的首次EXAFS / XANES研究，因此，这些数据应为以后通过这种方法对此类配合物进行研究设定基准。