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Structure and Spectroelectrochemical Response of Arene-Ruthenium and Arene-Osmium Complexes with Potentially Hemilabile Noninnocent Ligands

, , , , , , , , und . Organometallics 33 (18): 4973--4985 (2014)

Zusammenfassung

Nine derivs. of M(L2-)(p-cymene) (M = Ru, Os, L2- = 4,6-di-tert-butyl-N-aryl-o-amidophenolate) were prepd. and structurally characterized (Ru complexes) as coordinatively unsatd., formally 16 valence electron species. On L2--ligand based oxidn. to EPR-active iminosemiquinone radical complexes, the compds. 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 spectroelectrochem. at ambient and low temps. in combination with DFT results confirm a square scheme behavior (ECEC mechanism) involving the ligand as the main electron transfer site and the metal with fractional (d) oxidn. as the center for redox-activated coordination. Attempts to crystallize Ru(Cym)(QSMe)(PF6) (QSMe = 4,6-di-tert-butyl-2-(2-methylthiophenyl)amidophenolate) produced single crystals of RuIII(QSMe.bul.-)2(PF6) after apparent dissocn. of the arene ligand. on SciFinder(R)

Links und Ressourcen

DOI:
10.1021/om5002815
BibTeX-Schlüssel:
Bubrin.2014
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