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 [Ru(II)([9]aneS3)(L)(dmso)]ClO4 ([]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)Ru(III)-L˙](3+) (1(3+)) ⇌ [([9]aneS3)(dmso)Ru(III)-L(-)](2+)/[([9]aneS3)(dmso)Ru(II)-L˙](2+) (1(2+)) ⇌ [([9]aneS3)(dmso)Ru(II)-L(-)](+) (1(+)) ⇌ [([9]aneS3)(dmso)Ru(II)-L(˙2-)] (1) ⇌ [([9]aneS3)(dmso)Ru(II)-L(3-)](-)/[([9]aneS3)(dmso)Ru(I)-L(˙2-)](-) (1-).
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-400076, India. lahiri@chem.iitb.ac.in.
Hemlata
H
Agarwala
Thomas Michael
TM
Scherer
Shaikh M
SM
Mobin
Wolfgang
W
Kaim
Goutam Kumar
GK
Lahiri