| dc.creator |
Kinunda, Grace |
|
| dc.creator |
Jaganyi, Deogratias |
|
| dc.date |
2018-09-19T11:59:37Z |
|
| dc.date |
2018-09-19T11:59:37Z |
|
| dc.date |
2014 |
|
| dc.date.accessioned |
2021-05-03T13:19:55Z |
|
| dc.date.available |
2021-05-03T13:19:55Z |
|
| dc.identifier |
G Kinunda, D Jaganyi - Transition Metal Chemistry, 2014 - Springer |
|
| dc.identifier |
http://hdl.handle.net/20.500.11810/4913 |
|
| dc.identifier |
10.1007/s11243-014-9819-8 |
|
| dc.identifier.uri |
http://hdl.handle.net/20.500.11810/4913 |
|
| 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.subject |
Metal Centre |
|
| dc.subject |
Density Functional Theory Calculation |
|
| dc.subject |
Terpy |
|
| dc.subject |
Electronic Supplementary Information |
|
| dc.subject |
Quinoline Moiety |
|
| dc.title |
Understanding the Electronic and π-conjugation Roles of Quinoline on Ligand Substitution Reactions of Pt(II) Complexes |
|
| dc.type |
Journal Article, Peer Reviewed |
|