Issue 7, 1976

Kinetic studies on closure of a second condensed ring in [bis(2-aminoethyl) methylamine hydrochloride]dichloro- and dichloro[tris(2-aminoethyl)amine bis(hydrochloride)]-platinum(II) complexes

Abstract

The title complexes [PtCl2(bama·HCl)] and [PtCl2(taa·2HCl)] with the tri- and quadri-dentate ligands acting as bidentate have been prepared and the kinetics of closure of the second condensed ring have been studied in aqueous solution. From stopped-flow measurements in basic media at 25 °C, the rate constants for the reactions [PtCl2-(bama)][PtCl(bama)]++ Cl and [PtCl2(taa)][PtCl(taa)]++ Cl are k1= 2.1 ± 0.1 and k1″= 4.3 ± 0.2 s–1. This implies that only a probability factor of two can satisfactorily account for the difference in the observed rates. Kinetic measurements at pH < 7 have show that under these conditions the reactive species are unprotonated [PtCl2(bama)] and monoprotonated [PtCl2(taa·HCl)]; the ring-closure process is faster for the tris(2-aminoethyl)amine (taa) complex than for the bis(2-aminoethyl)methylamine (bama) complex, and anchimeric assistance of the protonated end of taa on entry of the unprotonated end (by ion pairing with the leaving chloride) is proposed.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1976, 626-631

Kinetic studies on closure of a second condensed ring in [bis(2-aminoethyl) methylamine hydrochloride]dichloro- and dichloro[tris(2-aminoethyl)amine bis(hydrochloride)]-platinum(II) complexes

G. Natile, G. Albertin, E. Bordignon and A. A. Orio, J. Chem. Soc., Dalton Trans., 1976, 626 DOI: 10.1039/DT9760000626

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