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Five diruthenium(II) complexes [Cl(L)Ru(μ-tppz)Ru(L)Cl] (1-5) containing differently substituted β-diketonato derivatives (1: L = 2,4-pentanedionato; 2: L = 3,5-heptanedionato; 3: L = 2,2,6,6-tetramethyl-3,5-heptanedionato; 4: L = 3-methyl-2,4-pentanedionato; 5: L = 3-ethyl-2,4-pentanedionato) as ancillary ligands (L) were synthesized and studied by spectroelectrochemistry (UV-Vis-NIR, electron paramagnetic resonance (EPR)). X-ray structural characterisation revealed anti (1, 2, 5) or syn (3) configuration as well as non-planarity of the bis-tridentate tppz bridge and strong dπ(Ru(II)) → π*(pyrazine, tppz) back-bonding. The widely separated one-electron oxidation steps, Ru(II)Ru(II)/Ru(II)Ru(III) and Ru(II)Ru(III)/Ru(III)Ru(III), result in large comproportionation constants (K(c)) of ≥10(10) for the mixed-valent intermediates. The syn-configurated (n) exhibits a particularly high K(c) of 10(12) for n = 1+, accompanied by density functional theory (DFT)-calculated minimum Ru-N bond lengths for this Ru(II)Ru(III) intermediate. The electrogenerated mixed-valent states 1(+)-5(+) exhibit anisotropic EPR spectra at 110 K with average values &lt;g&gt; of 2.304-2.234 and g anisotropies Δg = g(1)-g(3) of 0.82-0.99. Metal-to-metal charge transfer (MMCT) absorptions occur for 1(+)-5(+) in the NIR region at 1660 nm-1750 nm (ε ≈ 2700 dm(3) mol(-1) cm(-1), Δν(1/2) ≈ 1800 cm(-1)). DFT calculations of 1(+) and 3(+) yield comparable Mulliken spin densities of about 0.60 for the metal ions, corresponding to valence-delocalised situations (Ru(2.5))(2). Rather large spin densities of about -0.4 were calculated for the tppz bridges in 1(+) and 3(+). The calculated electronic interaction values (V(AB)) for 1(+)-5(+) are about 3000 cm(-1), comparable to that for the Creutz-Taube ion at 3185 cm(-1). The DFT calculations predict that the Ru(III)Ru(III) forms in 1(2+)-5(2+) prefer a triplet (S = 1) ground state with ΔE (S = 0 - S = 1) ∼5000 cm(-1). One-electron reduction takes place at the tppz bridge which results in species [Cl(L)Ru(II)(μ-tppz˙(-))Ru(II)(L)Cl](-) (1˙(-)-3˙(-), 5˙(-)) which exhibit free radical-type EPR signals and NIR transitions typical of the tppz radical anion. The system 4(n) is distinguished by lability of the Ru-Cl bonds.

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Strong metal–metal coupling in mixed-valent intermediates [Cl(L)Ru(μ-tppz)Ru(L)Cl]+, L = β-diketonato ligands, tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine