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Issue 10, 2014
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Bidirectional non-innocence of the β-diketonato ligand 9-oxidophenalenone (L) in [Ru([9]aneS3)(L)(dmso)]n, [9]aneS3 = 1,4,7-trithiacyclononane

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Abstract

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 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 0.77 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 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 behaviour of coordinated L˙/−/˙2−. Specifically, the studies establish significant involvement of L based frontier 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).

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

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Publication details

The article was received on 30 Oct 2013, accepted on 20 Dec 2013 and first published on 02 Jan 2014


Article type: Paper
DOI: 10.1039/C3DT53069H
Citation: Dalton Trans., 2014,43, 3939-3948
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    Bidirectional non-innocence of the β-diketonato ligand 9-oxidophenalenone (L) in [Ru([9]aneS3)(L)(dmso)]n, [9]aneS3 = 1,4,7-trithiacyclononane

    H. Agarwala, T. M. Scherer, S. M. Mobin, W. Kaim and G. K. Lahiri, Dalton Trans., 2014, 43, 3939
    DOI: 10.1039/C3DT53069H

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