A Kinetic Study of Aqua Ligand Substitution in Dinuclear Pt(II) Complexes Containing Four Non-Coplanar Pyridine Ligands

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dc.contributor.authorKinunda, Grace
dc.contributor.authorJaganyi, Deogratias
dc.date.accessioned2018-09-19T12:04:29Z
dc.date.available2018-09-19T12:04:29Z
dc.date.issued2014
dc.description.abstractSubstitution reactions of the aqua ligands from azine-bridged dinuclear platinum(II) complexes of the type [{cis-Pt(py)2(OH2)} 2(μ-pzn)](ClO4)4 [pzn = pyrazine (Pt-PZN), 2,3-dimethylpyrazine (Pt-2,3PZN), 2,5-dimethylpyrazine (Pt-2,5PZN) or 2,6-dimethylpyrazine (Pt-2,6PZN)] by thiourea nucleophiles were investigated under pseudo first-order conditions as a function of concentration and temperature using the stopped-flow technique. The experimental results are discussed in reference to structures obtained by DFT calculations. The results are in good agreement with the pKa values of the complexes as well as DFT calculations. Compared to [{cis/trans-Pt(NH3)2(OH2)} 2(μ-pzn)](ClO4)4, the complexes in this series react faster by a factor of 10 or 23 respectively due to the presence of pyridine rings, which forces the geometry to allow π-back bonding to take place such that the electrons from the metal centres are accepted to the empty π*-orbitals of the pyridine subunits. The reactivity of the nucleophile is sterically dependent, with N,N,N′,N′-tetramethylthiourea reacting three times slower than thiourea. In all complexes and for both substitution steps, the mode of activation remains associative in nature.en_US
dc.identifier.citationG Kinunda, D Jaganyi - Transition Metal Chemistry, 2014 - Springeren_US
dc.identifier.doi10.1007/s11243-014-9879-9
dc.identifier.urihttp://hdl.handle.net/20.500.11810/4916
dc.language.isoenen_US
dc.publisherSpringeren_US
dc.subjectMetal Centreen_US
dc.subjectPyrazineen_US
dc.subjectDinuclear Complexen_US
dc.subjectAqua Liganden_US
dc.subjectElectrophilicity Indexen_US
dc.titleA Kinetic Study of Aqua Ligand Substitution in Dinuclear Pt(II) Complexes Containing Four Non-Coplanar Pyridine Ligandsen_US
dc.typeJournal Article, Peer Revieweden_US
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