Key points are not available for this paper at this time.
The complexes Ru(tpy)(acac)(Cl), Ru(tpy)(acac)(H(2)O)(PF(6)) (tpy = 2,2',2"-terpyridine, acacH = 2,4 pentanedione) Ru(tpy)(C(2)O(4))(H(2)O) (C(2)O(4)(2)(-) = oxalato dianion), Ru(tpy)(dppene)(Cl)(PF(6)) (dppene = cis-1,2-bis(diphenylphosphino)ethylene), Ru(tpy)(dppene)(H(2)O)(PF(6))(2), Ru(tpy)(C(2)O(4))(py), Ru(tpy)(acac)(py)(ClO(4)), Ru(tpy)(acac)(NO(2)), Ru(tpy)(acac)(NO)(PF(6))(2), and Ru(tpy)(PSCS)Cl (PSCS = 1-pyrrolidinedithiocarbamate anion) have been prepared and characterized by cyclic voltammetry and UV-visible and FTIR spectroscopy. Ru(tpy)(acac)(NO(2))(+) is stable with respect to oxidation of coordinated NO(2)(-) on the cyclic voltammetric time scale. The nitrosyl Ru(tpy)(acac)(NO)(2+) falls on an earlier correlation between nu(NO) (1914 cm(-)(1) in KBr) and E(1/2) for the first nitrosyl-based reduction 0.02 V vs SSCE. Oxalate ligand is lost from Ru(II)(tpy)(C(2)O(4))(H(2)O) to give Ru(tpy)(H(2)O)(3)(2+). The Ru(III/II) and Ru(IV/III) couples of the aqua complexes are pH dependent. At pH 7.0, E(1/2) values are 0.43 V vs NHE for Ru(III)(tpy)(acac)(OH)(+)/Ru(II)(tpy)(acac)(H(2)O)(+), 0.80 V for Ru(IV)(tpy)(acac)(O)(+)/Ru(III)(tpy)(acac)(OH)(+), 0.16 V for Ru(III)(tpy)(C(2)O(4))(OH)/Ru(II)(tpy)(C(2)O(4))(H(2)O), and 0.45 V for Ru(IV)(tpy)(C(2)O(4))(O)/Ru(III)(tpy)(C(2)O(4))(OH). Plots of E(1/2) vs pH define regions of stability for the various oxidation states and the pK(a) values of aqua and hydroxo forms. These measurements reveal that C(2)O(4)(2)(-) and acac(-) are electron donating to Ru(III) relative to bpy. Comparisons with redox potentials for 21 related polypyridyl couples reveal the influence of ligand changes on the potentials of the Ru(IV/III) and Ru(III/II) couples and the difference between them, DeltaE(1/2). The majority of the effect appears in the Ru(III/II) couple. ()A linear correlation exists between DeltaE(1/2) and the sum of a set of ligand parameters defined by Lever et al., SigmaE(i)(L(i)), for the series of complexes, but there is a dramatic change in slope at DeltaE(1/2) approximately -0.11 V and SigmaE(i)(L(i)) = 1.06 V. Extrapolation of the plot of DeltaE(1/2) vs SigmaE(i)(L(i)) suggests that there may be ligand environments in which Ru(III) is unstable with respect to disproportionation into Ru(IV) and Ru(II). This would make the two-electron Ru(IV)O/Ru(II)OH(2) couple more strongly oxidizing than the one-electron Ru(IV)O/Ru(III)OH couple.
Dovletoglou et al. (1996) studied this question.