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dc.contributor.authorBerners-Price, Sueen_US
dc.contributor.authorW. Cox, Johnen_US
dc.contributor.authorBarklage, Walter.en_US
dc.contributor.authorQu, Yun.en_US
dc.contributor.authorFarrell, Nicholas.en_US
dc.date.accessioned2017-09-25T12:30:46Z
dc.date.available2017-09-25T12:30:46Z
dc.date.issued2000en_US
dc.date.modified2007-03-13T21:51:42Z
dc.identifier.issn0020-1669en_US
dc.identifier.doi10.1021/ic991104hen_US
dc.identifier.urihttp://hdl.handle.net/10072/3212
dc.description.abstractBy the use of [1H,15N] heteronuclear single quantum coherence (HSQC) 2D NMR spectroscopy and electrochemical methods we have determined the hydrolysis profile of the bifunctional dinuclear platinum complex [{trans-PtCl(15NH3)2}2(μ-15NH2(CH2)615NH2)]2+ (1,1/t,t (n = 6), 15N-1), the prototype of a novel class of potential antitumor complexes. Reported are estimates for the rate and equilibrium constants for the first and second aquation steps, together with the acid dissociation constant (pKa1 ≈ pKa2 ≈ pKa3). The equilibrium constants determined by NMR at 25 and 37 °C (I = 0.1 M) were similar, pK1 ≈ pK2 = 3.9 ± 0.2, and from a chloride release experiment at 37 °C the values were found to be pK1 = 4.11 ± 0.05 and pK2 = 4.2 ± 0.5. The forward and reverse rate constants for aquation determined from this chloride release experiment were k1 = (8.5 ± 0.3) × 10-5 s-1 and k-1 = 0.91 ± 0.06 M-1 s-1, where the model assumed that all the liberated chloride came from 1. When the second aquation step was also taken into account, the rate constants were k1 = (7.9 ± 0.2) × 10-5 s-1, k-1 = 1.18 ± 0.06 M-1 s-1, k2 = (10.6 ± 3.0) × 10-4 s-1, k-2 = 1.5 ± 0.6 M-1 s-1. The rate constants compare favorably with other complexes with the [PtCl(am(m)ine)3]+ moiety and indicate that the equilibrium of all these species favors the chloro form. A pKa value of 5.62 was determined for the diaquated species [{trans-Pt(15NH3)2(H2O)}2(μ-15NH2(CH2)615NH2)]4+ (3) using [1H,15N] HSQC NMR spectroscopy. The speciation profile of 1 and its hydrolysis products under physiological conditions is explored.en_US
dc.description.peerreviewedYesen_US
dc.description.publicationstatusYesen_AU
dc.languageEnglishen_US
dc.language.isoen_AU
dc.publisherAmerican Chemical Societyen_US
dc.publisher.placeUSAen_US
dc.relation.ispartofpagefrom1710en_US
dc.relation.ispartofpageto1715en_US
dc.relation.ispartofjournalInorganic Chemistryen_US
dc.relation.ispartofvolume39No 8en_US
dc.subject.fieldofresearchHISTORY AND ARCHAEOLOGYen_US
dc.subject.fieldofresearchcode210000en_US
dc.titleEquilibrium and Kinetic Studies of the Aquation of the Dinuclear Platinum Complex ({trans-PtCI(NH3)2}2(uNH2(CH2)2+:pK Determinations of Aqua Ligands via (1H, 15N)NMR Spectroscopyen_US
dc.typeJournal articleen_US
dc.type.descriptionC1 - Peer Reviewed (HERDC)en_US
dc.type.codeC - Journal Articlesen_US
gro.facultyGriffith Sciences, Griffith Institute for Drug Discoveryen_US
gro.date.issued2000
gro.hasfulltextNo Full Text


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