Synthesis and characterization of dinuclear complexes of 3,3',4,4'-tetraminobiphenyl with tetramminoruthenium and bis(bipyridine)-ruthenium residues and their two- and four-electron oxidized products including a ZINDO study of orbital mixing as a fun

摘要

This paper reports the synthesis, characterisation and reactivity of new complexes of ruthenium, the symmetric dinuclear complex of ruthenium tetrammine [(Ru(NH_3)_4)_2(catH_4 centre dot catH_4)](PF_6)_4 and the asymmetric dinuclear complex of ruthenium bis(bipyridine) and ruthenium tetrammine [Ru(NH_3)_4(catH_4 centre dot catH_4)Ru(bpy(_2][PF_6)_4 where (catH_4 centre dot catH_4) represents the bridging ligand 3,3',4,4'-tetraminobiphenyl. These complexes can be oxidized to the two-electron oxidized ligand mixed valence (qH_2 centre dot catH_4) species and the four-electron oxidized ligand (aH_2 centre dot aH_2) species. Further oxidation yields a range of Ru(III) species. These complexes were studied by proton NMR, UV-VIS spectra, cyclic voltammetry and ZINDO/1 and ZINDO/S calculations.