Abstract
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)
Users
Please
log in to take part in the discussion (add own reviews or comments).