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Title: Silver(I)-catalysed abstraction of coordinated cyanide in hexacyanoferrate(II) by D-penicillamine in aqueous medium
Authors: Naik, R M
Tiwari, R K
Yadav, S B S
Kumar, B
Asthana, A
Keywords: D-penicillamine;Hexacyanoferrate(II);Kinetics;Spectrophotometry
Issue Date: Jul-2012
Publisher: NISCAIR-CSIR, India
Abstract: The kinetics and mechanism of Ag(I)-catalyzed exchange of coordinated cyanide in hexacyanoferrate(II) by D-penicillamine (D-PA) have been monitored by following the appearance of blue colored complex [Fe(CN)5(D-PA)]3-at 423 nm, corresponding to metal to ligand charge transfer (MLCT) transition. The effect of pH, ionic strength, catalyst concentration and concentration of hexacyanoferrate(II) and D-penicillamine on the rate of reaction has also studied and explained. The findings indicate first order dependence each in [Fe(CN)6]4- and [D-PA]. The composition of the complex formed has been established to be 1:1 by mole ratio and slope ratio method. The kinetic observations suggest that the substitution follows an interchange dissociative (Id) mechanism which proceeds via formation of a solvent bound intermediate. The activation parameters ΔH# and ΔS# have also been calculated and provided in support of the proposed mechanistic scheme. It is observed first time that the drug D-penicillamine used acts as a potential ligand and it can replace the coordinated cyanide in hexacyanoferrate(II).
Page(s): 250-256
ISSN: 0975-0991 (Online); 0971-457X (Print)
Appears in Collections:IJCT Vol.19(4) [July 2012]

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