Structure and Spectroelectrochemical Response of Arene鈥揜uthenium and Arene鈥揙smium Complexes with Potentially Hemilabile Noninnocent Ligands

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• 作者：Martina Bubrin ; David Schweinfurth ; Fabian Ehret ; Stanislav Z谩li拧 ; Hana Kvapilov谩 ; Jan Fiedler ; Qiang Zeng ; Franti拧ek Hartl ; Wolfgang Kaim
• 刊名：Organometallics
• 出版年：2014
• 出版时间：September 22, 2014
• 年：2014
• 卷：33
• 期：18
• 页码：4973-4985
• 全文大小：712K
• ISSN：1520-6041

文摘

Nine of the compounds [M(L^{2鈥?/sup>)(p-cymene)] (M = Ru, Os, L2鈥?/sup> = 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鈥?/sup>-ligand based oxidation to EPR-active iminosemiquinone radical complexes, the compounds seek to bind a donor atom (if available) from the N-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 Ln ligand as the main electron transfer site and the metal with fractional (未) oxidation as the center for redox-activated coordination. Attempts to crystallize [Ru(Cym)(Q_SMe)](PF₆) produced single crystals of [RuIII(Q_SMe鈥⑩€?/sup>)₂](PF₆) after apparent dissociation of the arene ligand.}