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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