Jump to main content
Jump to site search

Issue 35, 2012
Previous Article Next Article

The π-acceptor effect in the substitution reactions of tridentate N-donor ligand complexes of platinum(II): a detailed kinetic and mechanistic study

Author affiliations

Abstract

The nucleophilic substitution reactions of complexes [Pt{4′-(2′′′-CH3-phenyl)-2,2′:6′,2′′-terpyridine}Cl]CF3SO3, [CH33PhPtCl], [Pt{4′-(2′′′-CH3-phenyl)-6-(3′′-isoquinoyl)-2,2′bipyridine}Cl]SbF6, [CH33PhisoqPtCl], [Pt{2-(2′-pyridyl)-1,10-phenanthroline}Cl]Cl, [pyPhenPtCl], and [Pt(terpyridine)Cl]+, [PtCl] with a series of nucleophiles: thiourea (TU), N,N-dimethylthiourea (DMTU), N,N,N,N-tetramethylthiourea (TMTU), I, Br, and SCN were studied in 0.1 M LiCF3SO3 in methanol (in the presence of 10 mM LiCl). The reactivity of the investigated complexes follows the order pyPhenPtCl > PtCl > CH33PhPtCl > CH33PhisoqPtCl. The lability of the chloride ligand is dependent on the strength of π-backbonding properties of the spectator ligands around the platinum centre. The experimental data is strongly supported by DFT calculations. The dependence of the second-order rate constants on concentration of the nucleophiles as well as the large negative values reported for the activation entropy (ΔS) confirmed an associative mechanism of substitution.

Graphical abstract: The π-acceptor effect in the substitution reactions of tridentate N-donor ligand complexes of platinum(ii): a detailed kinetic and mechanistic study

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 14 May 2012, accepted on 18 Jun 2012 and first published on 19 Jun 2012


Article type: Paper
DOI: 10.1039/C2DT31041D
Citation: Dalton Trans., 2012,41, 10724-10730
  •   Request permissions

    The π-acceptor effect in the substitution reactions of tridentate N-donor ligand complexes of platinum(II): a detailed kinetic and mechanistic study

    P. Ongoma and D. Jaganyi, Dalton Trans., 2012, 41, 10724
    DOI: 10.1039/C2DT31041D

Search articles by author