Structure, spectra and electrochemistry of ruthenium-carbonyl complexes of naphthylazoimidazole

• Published in: Inorganica Chimica Acta 2008-06, Vol.361 (8), p.2431-2438
• Main Authors: Mondal, Tapan Kumar, Dinda, Joydev, Cheng, Jack, Lu, Tian-Huey, Sinha, Chittaranjan
• Format: Article
• Language: English
• Subjects: DFT calculation; Electrochemistry; Naphthylazoimidazoles; Ruthenium-carbonyl-hydride; X-ray structure
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2007.12.026

The synthesis of [Ru(H)(CO)(PPh 3) 2(α/β-NaiR)](ClO 4), [Ru(Cl)(CO)(PPh 3) 2(α/β-NaiR)](ClO 4), are described in this work (α/β-NaiR = 1-alkyl-2-(naphthyl-α/β-azo)imidazole). The X-ray structure of [Ru(H)(CO)(PPh 3) 2(α/β-NaiMe)](ClO 4) is described. Presence of C–H–π interactions between two adjacent molecules has generated non-covalent dimer. Cyclic voltammogram of the complexes report metal oxidation and ligand reductions. DFT calculation defines electronic structures, charge transfer transition and redox properties of the complexes in gas phase. [Ru(H)(CO)(PPh 3) 2(α/β-NaiR)](ClO 4) ( 3, 4) are synthesized by the reaction of [Ru(H)(Cl)(CO)(PPh 3) 3] with 1-alkyl-2-(naphthyl-α/β-azo)imidazole (α-NaiR ( 3); β-NaiR ( 4)). One of the complexes [Ru(H)(CO)(PPh 3) 2(α-NaiMe)](ClO 4) ( 3a) has been structurally established by X-ray diffraction study. Upon addition of Cl 2 saturated in MeCN to 3 or 4 gives [Ru(Cl)(CO)(α/β-NaiR)(PPh 3) 2](ClO 4) (for α-NaiR ( 5); β-NaiR ( 6)), without affecting metal oxidation state, which were characterized by spectroscopic measurements. The redox property of the complexes is examined by cyclic voltammetry.