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Kinetics of chloride substitution in [Pt(bpma)Cl]+ and [Pt(gly-met-S,N,N)Cl] complexes by thiourea, nitrites, and iodides

Adrian Topolski and Živadin Bugarčić

Faculty of Chemistry, Nicolaus Copernicus University, Gagarina 7, 87-100, Toruń, Poland

 

E-mail: topolski@umk.pl

Abstract: Substitution of chloride in [PtCl(bpma)]+ and [PtCl(gly-met-S,N,N)], where bpma is bis(2-pyridylmethyl)amine and gly-met-S,N,N is glycyl-l-methionine, was studied as a function of the entering nucleophile concentration and temperature. Reactions between the platinum(II) complexes and thiourea (TU), iodides (I), and nitrites(III) (NO 2 ) were carried out in aqueous solutions using conventional UV-VIS spectrophotometry. Suitable ionic conditions were reached by an addition of 0.1 M NaClO4 and 0.01 M NaCl (to suppress hydrolysis). The second-order rate constants, k 2, for the studied reactions with NO 2 varied between 0.036–0.038 M−1 s−1, and for the reactions with TU between 0.095–1.06 M−1 s−1, respectively. The reaction between TU and the [PtCl(bpma)]+ ion is ten times faster than that of the [PtCl(gly-met-S,N,N)] complex. An analysis of the activation parameters, ΔH and ΔS , for the selected reactions clearly shows their associative nature.

Keywords: platinum(II) complexes – substitution – kinetics – thiourea – nitrites(III) – iodides

Full paper is available at www.springerlink.com.

DOI: 10.2478/s11696-013-0418-5

 

Chemical Papers 68 (1) 130–135 (2014)

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