Structure and spectroelectrochemical response of arene− ruthenium and arene−osmium complexes with potentially hemilabile noninnocent ligandsBubrin, M., Schweinfurth, D., Ehret, F., Záliš, S., Kvapilová, H., Fiedler, J., Zeng, Q., Hartl, F. and Kaim, W. (2014) Structure and spectroelectrochemical response of arene− ruthenium and arene−osmium complexes with potentially hemilabile noninnocent ligands. Organometallics, 33 (18). pp. 4973-4985. ISSN 1520-6041 Full text not archived in this repository. It is advisable to refer to the publisher's version if you intend to cite from this work. See Guidance on citing. To link to this item DOI: 10.1021/om5002815 Abstract/SummaryNine 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 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 (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.
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