Bidirectional non-innocence of the b-diketonato ligand 9-oxidophenalenone (L-) in Ru(9aneS3)(L)(dmso)n, 9aneS3 = 1,4,7-trithiacyclononane
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Dalton Transactions 43 (10): 3939--3948 (2014)

RuII(9aneS3)(L)(DMSO)ClO4 (1ClO4) (9aneS3 = 1,4,7-trithiacyclononane, HL = 9-hydroxyphenalenone, DMSO = DMSO) was structurally characterized to reveal almost equal C-O bond distances of coordinated L-, suggesting a delocalized bonding situation of the b-diketonato ligand. The DMSO ligand is coordinated via the sulfur atom in the native (1+) and reduced states (1 and 1-) as was revealed by x-ray crystallog. and by DFT calcns. Cyclic voltammetry of 1+ exhibits two close-lying 1-electron oxidn. waves at 0.77 V and 0.94 V, and two similarly close 1-electron redn. processes at -1.43 V and -1.56 V vs. SCE in CH2Cl2. The electronic structures of 1n in the accessible redox states were analyzed via expts. (EPR and UV-visible-NIR spectroelectrochem.) and by DFT/TD-DFT calcns., revealing the potential for bidirectional noninnocent behavior of coordinated L·/-/·2-. Specifically, the studies establish significant involvement of L based frontier orbitals in both the oxidn. and redn. processes: (9aneS3)(DMSO)RuIII-L·3+ (13+) .dblharw. (9aneS3)(DMSO)RuIII-L-2+/(9aneS3)(DMSO)RuII-L·2+ (12+) .dblharw. (9aneS3)(DMSO)RuII-L-+ (1+) .dblharw. (9aneS3)(DMSO)RuII-L·2- (1) .dblharw. (9aneS3)(DMSO)RuII-L3--/(9aneS3)(DMSO)RuI-L·2-- (1-). on SciFinder(R)
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