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Issue 6, 2014
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Kinetic and mechanistic studies of 1,3-bis(2-pyridylimino)isoindolate Pt(II) derivatives. Experimental and new computational approach

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Abstract

The rate of substitution of the chloride ligand by three bio-relevant nucleophiles, thiourea (Tu), N,N-dimethylthiourea (Dmtu) and N,N,N,N-tetramethylthiourea (Tmtu), in the complexes: 1,3-bis(2-pyridylimino)isoindoline platinum(II) chloride (Pt2), 1,3-bis(2-pyridylimino)benz(f)isoindoline platinum(II) chloride (Pt3) and 1,3-bis(1-isoquinolylimino)isoindoline platinum(II) complex (Pt4) was investigated under pseudo first-order conditions as a function of concentration and temperature using stopped-flow and UV-Visible spectrophotometry. Computational modeled data of bis(pyridylimino)3,4-pyrrolate platinum(II) chloride (Pt1) were incorporated in the study for comparison. The observed pseudo first-order rate constants for substitution reactions obey the rate law kobs = k2[Nu]. High negative activation entropies and second-order kinetics for the displacement reactions all support an associative mode of activation. The reactivity is dependent on stabilization of the LUMO energy and inversely proportional to the number of phenyl rings added irrespective of the site of attachment. The electron density on the ligand moiety plays a significant role in the substitution behavior of the platinum(II) complexes, as supported by DFT descriptors {electrophilicity index (ω) and chemical hardness (η)}.

Graphical abstract: Kinetic and mechanistic studies of 1,3-bis(2-pyridylimino)isoindolate Pt(ii) derivatives. Experimental and new computational approach

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Publication details

The article was received on 20 Aug 2013, accepted on 18 Nov 2013 and first published on 19 Nov 2013


Article type: Paper
DOI: 10.1039/C3DT52272E
Citation: Dalton Trans., 2014,43, 2549-2558
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    Kinetic and mechanistic studies of 1,3-bis(2-pyridylimino)isoindolate Pt(II) derivatives. Experimental and new computational approach

    I. M. Wekesa and D. Jaganyi, Dalton Trans., 2014, 43, 2549
    DOI: 10.1039/C3DT52272E

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