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 [RuII([9]aneS3)(L)(dmso)]ClO4 ([1]ClO4) ([9]aneS3 = 1,4,7-trithiacyclononane, HL =9-hydroxyphenalenone, dmso = dimethylsulfoxide) has been structurally characterised to reveal almostequal C–O bond distances of coordinated L−, suggesting a delocalised bonding situation of the β-diketonatoligand. 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 of1+ exhibits two close-lying one-electron oxidation waves at 0.77 V and 0.94 V, and two similarly closeone-electron reduction processes at −1.43 V and −1.56 V versus SCE in CH2Cl2. The electronic structuresof 1n in the accessible redox states have been analysed via experiments (EPR and UV-vis-NIR spectroelectrochemistry)and by DFT/TD-DFT calculations, revealing the potential for bidirectional non-innocent behaviourof coordinated L•/−/•2−. Specifically, the studies establish significant involvement of L basedfrontier orbitals in both the oxidation and reduction processes: [([9]aneS3)(dmso)RuIII–L•]3+ (13+) ⇌ [([9]-aneS3)(dmso)RuIII–L−]2+/[([9]aneS3)(dmso)RuII–L•]2+ (12+) ⇌ [([9]aneS3)(dmso)RuII–L−]+ (1+) ⇌ [([9]aneS3)-(dmso)RuII–L•2−] (1) ⇌ [([9]aneS3)(dmso)RuII–L3−]−/[([9]aneS3)(dmso)RuI–L•2−]− (1−).

Ämnesord

NATURVETENSKAP  -- Kemi -- Oorganisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)

Nyckelord

Chemistry with specialization in Inorganic Chemistry

Kemi med inriktning mot oorganisk kemi

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