2,2'-Dipyridylketone (dpk) as ancillary acceptor and reporter ligand in complexes [(dpk)(Cl)Ru(mu-tppz)Ru(Cl)(dpk)]n+ where tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine

The tppz-bridged diruthenium(II) complex (dpk)(Cl)Ru(II)(mu-tppz)Ru(II)(Cl)(dpk)](ClO4)2, 2](ClO4)2, and mononuclear (dpk)(Cl)Ru(II)(tppz)](ClO4), 1](ClO4) tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, dpk = 2,2'-dipyridylketone], have been synthesized. The 260 mV separation between successive one-electron oxidation couples in 2]2+ translates to a relatively small comproportionation constant, Kc, of 2.5 x 10(4) for the intermediate. It is shown how electrochemical data (E(ox), E(red), Kc) reflect the donor/acceptor effects of ancillary ligands L in a series of systems (L)ClRu(mu-tppz)RuCl(L)]n, particularly the competition between L and tppz for electron density from the metal. According to EPR (g1 = 2.470, g2 = 2.195, and g3 = 1.873 at 4 K) the intermediate 2]3+ is a mixed-valent Ru(II)Ru(III) species which shows a rather narrow intervalence charge transfer (IVCT) band at 1800 nm (epsilon = 1500 M(-1) cm(-1)). The width at half-height (Deltanu(1/2)) of 700 cm(-1) of the IVCT band is much smaller than the calculated value of 3584 cm(-1), obtained by using the Hush formula Deltanu(1/2) = (2310E(op))(1/2) (E(op) = 5556 cm(-1), energy of the IVCT transition) which would be applicable to localized (Class II) mixed-valent Ru(II)Ru(III) systems. Valence delocalization in 2]3+ is supported by the uniform shift of the nu(C=O) band of the N,N'-coordinated dpk ligands from 1676 cm(-1) in the Ru(II)Ru(II) precursor to 1690 cm(-1) in the Ru(2.5)Ru(2.5) form, illustrating the use of the dpk acceptor to act as reporter ligand via the free but pi-conjugated organic carbonyl group. The apparent contradiction between the moderate value of Kc and the narrow IVCT band is being discussed considering "borderline" or "hybrid" "Class II-III" concepts of mixed-valency, as well as coordination aspects, i.e., the bis-tridentate nature of the pi-acceptor bridging ligand. Altogether, the complex ions 1]+ and 2]2+ display four and five successive reduction processes, respectively, involving both tppz- and dpk-based unoccupied pi orbitals. The one-electron reduced form 2]+ has been assigned as a tppz*- radical-anion-containing species which exhibits a free-radical-type EPR signal at 4K (g(parallel) = 2.002, g(perpendicular) = 1.994) and one moderately intense ligand-based low-energy band at 965 nm (epsilon = 1100 M(-1) cm(-1)).