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Azo compounds as electron acceptor or radical ligands in transition metal species: Spectroelectrochemistry and high-field EPR studies of ruthenium, rhodium and copper complexes of 2,2'-azobis(5-chloropyrimidine)

, , , , , , , , , , and . Journal of Molecular Structure, 656 (1-3): 183--194 (2003)
DOI: 10.1016/S0022-2860(03)00339-9

Abstract

Oxidative coupling of 2-aminopyrimidine with LiOCl produces 5-chloro-2,2'-azobis(pyrimidine) and 2,2'-azobis(5-chloropyrimidine) (abcp), both of which were structurally characterized. The sym. abcp was used as strongly p-accepting mono- and bis-chelate ligand in complexes with (bpy)2Ru2+, (H6C6)ClRu+, (Ph3P)2Cu+ and (OC)3ClRe. The p-acceptor capability of abcp results in low-energy MLCT transitions and facile redn. to isolable radical complexes of which the DFT-calcd. and structurally characterized dicopper(I) species (μ-abcp)Cu(PPh3)22(PF6) was studied by X- and W-band EPR and (μ-abcp)Ru(bpy)22(PF6)3 at 9.6, 230 and 285 GHz EPR frequency. The results indicate considerable metal-ligand orbital mixing in the singly occupied MOs. on SciFinder(R)

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