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Kinetics and mechanism of substitution reactions of the new bimetallic [{PdCl(bipy)}{mu-(NH2(CH2)(6)H2N)}{PtCl(biPY)}]Cl(ClO4) complex with important bio-molecules
dc.creator | Jovanović, Snežana | |
dc.creator | Petrović, Biljana | |
dc.creator | Petković, Marijana | |
dc.creator | Bugarčić, Živadin D. | |
dc.date.accessioned | 2018-03-01T16:33:34Z | |
dc.date.available | 2018-03-01T16:33:34Z | |
dc.date.issued | 2015 | |
dc.identifier.issn | 0277-5387 | |
dc.identifier.uri | https://vinar.vin.bg.ac.rs/handle/123456789/841 | |
dc.description.abstract | The new dinuclear bimetallic complex, [{PdCl(bipy)}{mu-(NH2(CH2)(6)H2N)}{PtCl(biPY)}]Cl(ClO4) (bipy is 2,2-bipyridine), has been prepared and characterized by elemental microanalysis, IR, H-1 NMR spectroscopy and MALDI-TOF mass spectrometry. Substitution reactions of the studied complex with selected biologically important ligands such as: thiourea (Tu), L-methionine (L-Met), L-cysteine (L-Cys), L-histidine (L-His) and guanosine-5-monophosphate (5-GMP), were studied under the pseudo-first order conditions as a function of concentration and temperature using stopped-flow and UV-Vis spectrophotometry. The reactions were monitored in 0.1 M NaClO4 at pH 5.0, in the presence of 40 mM NaCI. All fast reactions were monitored by stopped-flow at three temperatures (288 K, 298 K, 308 K) to determine the activation parameters, while the reactions studied by UV-Vis spectrophotometry were tested only at 298 K. Observed order of reactivity of the used ligands is: Tu GT L-Met GT L-Cys GT L-His GT 5-GMP. Substitution reactions of the investigated bimetallic complex with Tu, L-Cys and L-His were followed by degradation to the corresponding substituted mononuclear complexes of palladium (II) and platinum (II), [Pd(bipy)(Nu)(2)] and [Pt(bipy)(Nu)(2)] (where Nu = Tu, L-Cys, L-His), by releasing of the bridge ligand,1,6-diaminohexane. In contrast, during the substitution reactions with L-Met and 5-GMP, the structure of starting bimetallic complex was preserved and the process of degradation can be halted. The proposed pathways of the substitution reactions of [{PdCl(bipy)}{mu-(NH2(CH2)(6)H2N)}{PtCl(biPY)}]Cl(ClO4) complex with all selected ligands were confirmed by H-1 NMR spectroscopy at 295 K. Additionally, the two pK(a) values of studied diaqua complex, [(Pd(H2O)(bipy)}(mu-(NH2(CH2)(6)H2N)}(Pt(H2O)(biPY)}](4+), were determined by spectrophotometric pH titration. The large negative values for the entropy of activation, Delta S-not equal, support an associative substitution mechanism. (C) 2015 Elsevier Ltd. All rights reserved. | en |
dc.publisher | Elsevier | |
dc.relation | info:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172011/RS// | |
dc.rights | restrictedAccess | en |
dc.source | Polyhedron | en |
dc.subject | Platinum | en |
dc.subject | Palladium | en |
dc.subject | Kinetic | en |
dc.subject | Mechanism | en |
dc.subject | Bimetallic complex | en |
dc.title | Kinetics and mechanism of substitution reactions of the new bimetallic [{PdCl(bipy)}{mu-(NH2(CH2)(6)H2N)}{PtCl(biPY)}]Cl(ClO4) complex with important bio-molecules | en |
dc.type | article | en |
dc.rights.license | ARR | |
dcterms.abstract | Петковић Маријана; Јовановиц, Снезана; Бугарциц, Зивадин Д.; Петровиц, Биљана; | |
dc.citation.volume | 101 | |
dc.citation.spage | 206 | |
dc.citation.epage | 214 | |
dc.identifier.wos | 000366077600028 | |
dc.identifier.doi | 10.1016/j.poly.2015.09.021 | |
dc.citation.rank | M22 | |
dc.type.version | publishedVersion | |
dc.identifier.scopus | 2-s2.0-84942517617 |