Bhattacharya, Samaresh ; Pramanik, Nimai Chand. ; Pramanik, Kausikisankar ; Ghosh, Prasanta (1998) Chemistry of [Ru(tpy)(pap)(l′)n+ (tpy = 2,2′,6′,2″-terpyridine; pap = 2-(phenylazo)pyridine; L′ = Cl-, H2O, CH3CN, 4-picoline, N3-; n = 1,2). X-ray crystal structure of [Ru(tpy)(pap)(CH3CN)](ClO4)2 and catalytic oxidation of water to dioxygen by [Ru(tpy)(pap)(H2O)]2+ Polyhedron, 17 (9). pp. 1525-1534. ISSN 0277-5387
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Official URL: http://linkinghub.elsevier.com/retrieve/pii/S02775...
Related URL: http://dx.doi.org/10.1016/S0277-5387(97)00401-4
Abstract
The reaction of [Ru(tpy)Cl3] with pap has afforded [Ru(tpy)(pap)Cl]+ which has been isolated and characterized as the perchlorate salt. Treatment of [Ru(tpy)(pap)Cl]+ with Ag+ in aqueous solution gives[Ru(tpy)(pap)(H2O)]2+. This aquo-complex has been reacted with three monodentate ligands (L′ = CH3CN, 4-picoline and N3¯to afford complexes of type [Ru(tpy)(pap)(L′)]n+. Structure determination of [Ru(tpy)(pap) (CH3CN)](ClO4)2 by X-ray crystallography shows that tpy is coordinated to ruthenium in the usual meridional fashion and the pap ligand is bound to ruthenium with the azo-nitrogen trans to CH3CN. All these complexes except [Ru(tpy)(pap)H2O)]2+ show a Ru(II)-Ru(III) oxidation in the range 1.11-1.50 V vs SCE and three ligand(pap)/(tpy)-based reductions on the negative side of SCE. The aquo-complex shows a RuII---OH2/RuIV=O couple in aqueous solution (pH = 1-4), the E° of this oxidation is estimated to be 0.82 V vs SCE. Attempt to chemically oxidize the aquo-complex by Ce4+ in aqueous solution (1 M HClO4) results in the catalytic oxidation of water to dioxygen.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to Elsevier Science. |
| Keywords: | Ruthenium; 2-(phenylazo)pyridine; Synthesis; Characterization; Structure; Reactivities |
| ID Code: | 1886 |
| Deposited On: | 08 Oct 2010 12:29 |
| Last Modified: | 08 Oct 2010 12:29 |
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