Structure and Spectroelectrochemical Response of Arene-Ruthenium and Arene-Osmium Complexes with Potentially Hemilabile Noninnocent Ligands
Structure and Spectroelectrochemical Response of Arene-Ruthenium and Arene-Osmium Complexes with Potentially Hemilabile Noninnocent Ligands
复制标题
具有潜在半不稳定非无害配体的芳烃-钌和芳烃-锇配合物的结构和光谱电化学响应
DOI：
10.1021/om5002815
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发表时间：
2014
期刊：
影响因子：
2.8
通讯作者：
Bubrin M
中科院分区：
文献类型：
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作者：
Bubrin M
合成了9个化合物[M(L2-)(对伞花烃)](M=Ru，Os，L2-=4，6-二叔丁基-N-芳基-邻氨基苯酚)，其结构表征为配位不饱和，形式为16个价电子物种。在基于L2-配体的氧化为EPR活性的亚氨基半喹酮自由基络合物时，化合物寻求从当时的芳基取代基上结合一个给体原子(如果有)，如结构上证明的硫醚和硒醚功能，或从给体溶剂结合。模拟的循环伏安、常温和低温下的光谱电化学结合密度泛函的结果证实了以配体为主要电子转移中心和以部分(δ)氧化为中心进行氧化还原活化配位的方阵结构行为。尝试晶化[Ru(Cym)(QSMe)](PF6)，在芳烃配体明显解离后，得到了[RuIII(QSMe·-)2](PF6)的单晶。
Nine of the compounds [M(L2–)(p-cymene)] (M = Ru, Os, L2–= 4,6-di-tert-butyl-N-aryl-o-amidophenolate) were prepared and structurally characterized (Ru complexes) as coordinatively unsaturated, formally 16 valence electron species. On L2–-ligand based oxidation to EPR-active iminosemiquinone radical complexes, the compounds seek to bind a donor atom (if available) from theN-aryl substituent, as structurally certified for thioether and selenoether functions, or from the donor solvent. Simulated cyclic voltammograms and spectroelectrochemistry at ambient and low temperatures in combination with DFT results confirm a square scheme behavior (ECEC mechanism) involving the Lnligand as the main electron transfer site and the metal with fractional (δ) oxidation as the center for redox-activated coordination. Attempts to crystallize [Ru(Cym)(QSMe)](PF6) produced single crystals of [RuIII(QSMe•–)2](PF6) after apparent dissociation of the arene ligand.