Kinetic investigations of the mechanism of dihydrogen driven catalytic reduction of methylene blue, safranine O, methyl viologen and ferricyanide using platinum carbonyl cluster anions (Chini-clusters) as catalyst

Gupta, Nalinava Sen ; Mathur, Pradeep ; Mukesh, Doble ; Bhaduri, Sumit (2006) Kinetic investigations of the mechanism of dihydrogen driven catalytic reduction of methylene blue, safranine O, methyl viologen and ferricyanide using platinum carbonyl cluster anions (Chini-clusters) as catalyst Inorganica Chimica Acta, 359 (12). pp. 3895-3902. ISSN 0020-1693

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/S00201...

Related URL: http://dx.doi.org/10.1016/j.ica.2006.03.033

Abstract

[Bu4N]2[Pt12(CO)24] (1) catalyses the selective reduction of electron acceptors (S), methylene blue (MB+), safranine O (Saf+), methyl viologen (MV2+) and ferricyanide by dihydrogen. Macroscopic rate investigations for the cationic substrates in DMF, and for ferricyanide in DMSO have been carried out. In all cases, kobs is given by k1 [S] + k2, indicating that there are two catalytic cycles. In one of them, the formation of a complex between S and [Pt12(CO)24]2- in the rate determining step (rate constant k1) is followed by electron transfer and/or other fast steps. In the other catalytic cycle, the rate determining step (rate constant k2) involves formation of the solvated cluster anion [Pt12(CO)24]2-. The solvated cluster then undergoes fast reduction by dihydrogen and other reactions. The relative contributions of these two cycles depend on the substrate, and for MB+, Saf+, MV2+ and [Fe(CN)6]3- the contribution of the second cycle is about 99%, 55%, 77% and 97%, respectively. Both k1 and k2 of ferricyanide are about three orders of magnitude smaller than those of the cationic electron acceptors. The rates of reduction of MB+ and Saf+ have also been studied in the presence of added water. Rates increase as the presence of water provides an additional pathway for the reduction of [Pt12(CO)24]2- to [Pt9(CO)18]2-.

Item Type:Article
Source:Copyright of this article belongs to Elsevier Science.
Keywords:Chini Clusters; Kinetics; Catalysis; Reduction By Dihydrogen; Organic Dyes
ID Code:1970
Deposited On:08 Oct 2010 09:39
Last Modified:16 May 2016 13:01

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