Bidirectional non-innocence of the β-diketonato ligand 9-oxidophenalenone (L-) in [Ru([9]aneS3)(L)(dmso)]n, [9]aneS3 = 1,4,7-trithiacyclononane.

The new compound [Ru(II)([9]aneS3)(L)(dmso)]ClO4 ([]ClO4) ([9]aneS3 = 1,4,7-trithiacyclononane, HL = 9-hydroxyphenalenone, dmso = dimethylsulfoxide) has been structurally characterised to reveal almost equal C-O bond distances of coordinated L(-), suggesting a delocalised bonding situation of the β-diketonato ligand. The dmso ligand is coordinated via the sulfur atom in the native (1+) and reduced states (1 and 1-) as has been revealed by X-ray crystallography and by DFT calculations. Cyclic voltammetry of 1+ exhibits two close-lying one-electron oxidation waves at 0.

Experimental and DFT evidence for the fractional non-innocence of a β-diketonate ligand.

New compounds [Ru(pap)(2)(L)](ClO(4)), [Ru(pap)(L)(2)], and [Ru(acac)(2)(L)] (pap = 2-phenylazopyridine, L(-) = 9-oxidophenalenone, acac(-) = 2,4-pentanedionate) have been prepared and studied regarding their electron-transfer behavior, both experimentally and by using DFT calculations. [Ru(pap)(2)(L)](ClO(4)) and [Ru(acac)(2)(L)] were characterized by crystal-structure analysis. Spectroelectrochemistry (EPR, UV/Vis/NIR), in conjunction with cyclic voltammetry, showed a wide range of about 2 V for the potential of the Ru(III/II) couple, which was in agreement with the very different characteristics of the strongly π-accepting pap ligand and the σ-donating acac(-) ligand.

Application of a structure/oxidation-state correlation to complexes of bridging azo ligands.

Based on data from more than 40 crystal structures of metal complexes with azo-based bridging ligands (2,2'-azobispyridine, 2,2'-azobis(5-chloropyrimidine), azodicarbonyl derivatives), a correlation between the N-N bond lengths (d(NN)) and the oxidation state of the ligand (neutral, neutral/back-donating, radical-anionic, dianionic) was derived. This correlation was applied to the analysis of four ruthenium compounds of 2,2'-azobispyridine (abpy), that is, the new asymmetrical rac-[(acac)(2)Ru1(μ-abpy)Ru2(bpy)(2)](ClO(4))(2) ([1](ClO(4))(2)), [Ru(acac)(2)(abpy)] (2), [Ru(bpy)(2)(abpy)](ClO(4))(2) ([3](ClO(4))(2)), and meso-[(bpy)(2)Ru(μ-abpy)Ru(bpy)(2)(ClO(4))(3) ([4](ClO(4))(3); acac(-) =2,4-pentanedionato, bpy=2,2'-bipyridine). In agreement with DFT calculations, both mononuclear species 2 and 3(2+) can be described as ruthenium(II) complexes of unreduced abpy(0), with 1.

9-Oxidophenalenone: a noninnocent β-diketonate ligand?

The redox systems [Ru(L)(bpy)(2)](k), [Ru(L)(2)(bpy)](m), and [Ru(L)(3)](n) containing the potentially redox-active ligand 9-oxidophenalenone = L(-) were investigated by spectroelectrochemistry (UV-vis-near-IR and electron paramagnetic resonance) in conjunction with density functional theory (DFT) calculations. Compounds [Ru(L(-))(bpy)(2)]ClO(4) ([1]ClO(4)) and [Ru(L(-))(2)(bpy)]ClO(4) ([2]ClO(4)) were structurally characterized. In addition to establishing electron-transfer processes involving the Ru(II)/Ru(III)/Ru(IV) and bpy(0)/bpy(•-) couples, evidence for the noninnocent behavior of L(-) was obtained from [Ru(IV)(L(•))(L(-))(bpy)](3+), which exhibits strong near-IR absorption due to ligand-to-ligand charge transfer.

Asymmetrical diruthenium complex bridged by a redox-active ligand.

The asymmetrical dinuclear complex [(acac)(2)Ru1(μ-abpy)Ru2(Cym)Cl]PF(6) ([2]PF(6)), with acac(-) = acetylacetonato = 2,4-pentanedionato, abpy = 2,2'-azobis(pyridine), and Cym = p-cymene = 1-isopropyl-4-methylbenzene, has been obtained from the mononuclear precursors [Ru(acac)(2)(abpy)] and [Ru(Cym)Cl(2)](2). X-ray crystal structure analysis suggests the oxidation state formulation [(acac)(2)Ru1(III)(μ-abpy(•-))Ru2(II)(Cym)Cl](+) for 2(+), with antiferromagnetic coupling between one Ru(III) center and the radical-anion bridging ligand (abpy(•-)), based on the N-N distance of 1.352(3) Å.