| dc.creator |
Kinunda, Grace |
|
| dc.creator |
Jaganyi, Deogratius |
|
| dc.date |
2016-09-21T13:13:28Z |
|
| dc.date |
2016-09-21T13:13:28Z |
|
| dc.date |
2014-05-01 |
|
| dc.date.accessioned |
2018-03-27T08:55:03Z |
|
| dc.date.available |
2018-03-27T08:55:03Z |
|
| dc.identifier |
Kinunda, 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. |
|
| dc.identifier |
http://hdl.handle.net/20.500.11810/3898 |
|
| dc.identifier |
10.1007/s11243-014-9819-8 |
|
| dc.identifier.uri |
http://hdl.handle.net/20.500.11810/3898 |
|
| dc.description |
Full text can be accessed at
http://link.springer.com/article/10.1007/s11243-014-9819-8 |
|
| dc.description |
A 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. |
|
| dc.language |
en |
|
| dc.publisher |
Springer |
|
| dc.title |
Understanding the Electronic and Π-Conjugation Roles of Quinoline on Ligand Substitution Reactions of Platinum (II) Complexes |
|
| dc.type |
Journal Article, Peer Reviewed |
|