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Detailed mechanistic study on ligand substitution reactions in dinuclear platinum(II) complexes: effect of alkanediamine linker

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dc.contributor.authorOngoma, Peter O.
dc.contributor.authorJaganyi, Deogratius
dc.date.accessioned2024-06-14T10:19:46Z
dc.date.available2024-06-14T10:19:46Z
dc.date.issued2014-03-14
dc.description.abstractSubstitution of the coordinated water ligands from the cis-[{Pt(NH3)2H2O}2-μ-NH2(CH2) n NH2]4+ (n = 2–4, 6, 8, 10) complexes: EnPt, PropPt, ButPt, HexPt, OctPt and DecPt with S-donor nucleophiles thiourea, N,N-dimethyl-2-thiourea and N,N,N,N-tetramethyl-2-thiourea was studied under pseudo-first-order conditions as a function of concentration and temperature, using stopped-flow and UV–Vis Spectrophotometric techniques. The substitution reaction proceeded in two steps: simultaneous substitution of the aqua ligands, followed by the displacement of the ammine ligands in the trans-position due to the strong trans-effect of the coordinated thiourea nucleophiles, with each of the steps being sensitive to steric and σ-electronic properties of the alkanediamine linker. A comparison of the second-order rate constants, k 2,1st and k 2,2nd, indicates that the rate constants of the first step are 1–2 orders larger than those of the second step in all cases. The large negative ΔS ≠ values support an associative mode of substitution mechanism for both reaction steps. 1H and 195Pt NMR spectroscopy established that the α,ω-alkanediamine linkers remained coordinated to the metal centres, possibly due to their cis geometry to the incoming thiourea nucleophiles
dc.identifier.citationOngoma, P.O., Jaganyi, D. Detailed mechanistic study on ligand substitution reactions in dinuclear platinum(II) complexes: effect of alkanediamine linker. Transition Met Chem 39, 407–420 (2014). https://doi.org/10.1007/s11243-014-9815-z
dc.identifier.urihttps://doi.org/10.1007/s11243-014-9815-z
dc.identifier.urihttps://erepository.mku.ac.ke/handle/123456789/5910
dc.language.isoen
dc.publisherSpringer link
dc.subjectDinuclear Complex
dc.subjectDensity Function Theory
dc.subjectAqua Ligand
dc.subjectTMTU
dc.subjectDiaqua
dc.titleDetailed mechanistic study on ligand substitution reactions in dinuclear platinum(II) complexes: effect of alkanediamine linker
dc.typeArticle
dspace.entity.typePublication
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