Bidirectional non-innocence of the β-diketonato ligand 9-oxidophenalenone (L-) in [Ru(aneS3)(L)(dmso)]n, aneS3 = 1,4,7-trithiacyclononane
2014 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 43, 3939-3948 p.Article in journal (Refereed) Published
The new compound [RuII(aneS3)(L)(dmso)]ClO4 (ClO4) (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: [(aneS3)(dmso)RuIII–L•]3+ (13+) ⇌ [(-aneS3)(dmso)RuIII–L−]2+/[(aneS3)(dmso)RuII–L•]2+ (12+) ⇌ [(aneS3)(dmso)RuII–L−]+ (1+) ⇌ [(aneS3)-(dmso)RuII–L•2−] (1) ⇌ [(aneS3)(dmso)RuII–L3−]−/[(aneS3)(dmso)RuI–L•2−]− (1−).
Place, publisher, year, edition, pages
2014. Vol. 43, 3939-3948 p.
Research subject Chemistry with specialization in Inorganic Chemistry
IdentifiersURN: urn:nbn:se:uu:diva-236119DOI: 10.1039/c3dt53069hOAI: oai:DiVA.org:uu-236119DiVA: diva2:762765