Kinetic and Mechanistic Investigations on Some N,N‐Chelated Pt(II) Oxalate Complexes with Some “S” Containing Biorelevant Ligands at Physiological Condition |
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| Authors: | Sumon Ray Parnajyoti Karmakar Animesh Chattopadhyay Debabrata Nandi Roshni Sarkar Alak K Ghosh |
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| Institution: | 1. Department of Chemistry, The University of Burdwan, Burdwan, India;2. Department of Chemistry, Durgapur Government College, Durgapur, India |
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| Abstract: | The substitution of the chelating oxalate group by a group of nucleophiles, viz. thiourea (L1), 2‐thiouracil (L2), diethyldithiocarbamate (L3), dl ‐penicillamine (L4), and thiosemicarbazide (L5) was studied under pseudo–first‐order conditions as a function of concentration and temperature using UV–vis spectrophotometry and stopped‐flow technique. π‐Accepting effects are often used to account for the unusual high lability of Pt(bipy) complexes. The complexes Pt(dach)(oxalate)] (1) (dach = cis‐1,2‐diaminocyclohexane) and Pt(bipy)(oxalate)] (2) (bipy = 2,2'‐bipyridine) and substituted products were isolated and characterized by FTIR and ESI‐MS spectroscopic analysis. The negative entropies of activation support a strong contribution from bond making in the transition state of the substitution processes. |
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