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|Title:||Bidirectional non-innocence of the beta-diketonato ligand 9-oxidophenalenone (L-) in [Ru(aneS3)-(L)(dmso)](n), aneS3=1,4,7-trithiacyclononane|
|Publisher:||ROYAL SOC CHEMISTRY|
|Citation:||DALTON TRANSACTIONS, 43(10)3939-3948|
|Abstract:||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 almost equal C-O bond distances of coordinated L-, suggesting a delocalised bonding situation of the beta-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 0.77 V and 0.94 V, and two similarly close one-electron reduction processes at -1.43 V and -1.56 V versus SCE in CH2Cl2. The electronic structures of 1('') 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 behaviour of coordinated L(-/-/-)2(-). Specifically, the studies establish significant involvement of L based frontier orbitals in both the oxidation and reduction processes: [(aneS3)(dmso) Ru-III-L-](3+) (1(3+)). [(aneS3)(dmso) Ru-III-L-](2+)/[( aneS3)(dmso) Ru-II-L-](2+) (1(2+)). [( aneS3)(dmso) Ru-II-L-](+) (1(+)). [(aneS3)( dmso) Ru-II-L-2-] (1). [( aneS3)(dmso) Ru-II-L3-](-)/[( aneS3)(dmso) RuI-L-2-](-)(1(-)).|
|Appears in Collections:||Article|
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