Understanding the Electronic and Π-Conjugation Roles of Quinoline on Ligand Substitution Reactions of Platinum (II) Complexes

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dc.contributor.authorKinunda, Grace
dc.contributor.authorJaganyi, Deogratius
dc.date.accessioned2016-09-21T13:13:28Z
dc.date.available2016-09-21T13:13:28Z
dc.date.issued2014-05-01
dc.descriptionFull text can be accessed at http://link.springer.com/article/10.1007/s11243-014-9819-8en_US
dc.description.abstractA kinetic and mechanistic study of chloride substitution by thiourea nucleophiles, namely thiourea, N-methylthiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea in the complexes chlorobis-(2-pyridylmethyl)amineplatinum(II) (Pt1), chloro N-(2-pyridinylmethyl)-8-quinolinamineplatinum(II) (Pt2), chloro N-(2-pyridinylmethylene)-8-quinolinamineplatinum(II) (Pt3) and chlorobis(8-quinolinyl)amineplatinum(II) (Pt4) was undertaken under pseudo-first-order conditions using UV–visible spectrophotometry. The study showed that lability of the chloro leaving group is dependent on the strength of π-interactions between the filled dπ-orbitals of the metal and the empty π*-orbitals of the chelating ligand in the following manner: Pt1 > Pt3 > Pt2 > Pt4. Introduction of the quinoline moiety within the non-labile chelated framework of the Pt(II) complexes results in a more electron-rich metal centre which retards the approach of the nucleophile through repulsion. Moreover, the net σ-effect of the ligand moiety plays a significant role in controlling the reactivity of the complexes. The experimental results are interpreted with the aid of computational data obtained by density functional theory (B3LYP(CPCM)/LANL2DZp//B3LYP/-LANL2DZp) calculations. The mode of substitution remains associative as supported by negative entropies and the dependence of the second-order rate constants on the concentration of entering nucleophiles.en_US
dc.identifier.citationKinunda, G. and Jaganyi, D., 2014. Understanding the electronic and π-conjugation roles of quinoline on ligand substitution reactions of platinum (II) complexes. Transition Metal Chemistry, 39(4), pp.451-459.en_US
dc.identifier.doi10.1007/s11243-014-9819-8
dc.identifier.urihttp://hdl.handle.net/20.500.11810/3898
dc.language.isoenen_US
dc.publisherSpringeren_US
dc.titleUnderstanding the Electronic and Π-Conjugation Roles of Quinoline on Ligand Substitution Reactions of Platinum (II) Complexesen_US
dc.typeJournal Article, Peer Revieweden_US
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