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dc.contributor.authorRuhayel, Rasha A
dc.contributor.authorZgani, Ibrahim
dc.contributor.authorBerners-Price, Susan J
dc.contributor.authorFarrell, Nicholas P
dc.date.accessioned2018-02-15T01:00:21Z
dc.date.available2018-02-15T01:00:21Z
dc.date.issued2011
dc.date.modified2012-02-15T04:44:47Z
dc.identifier.issn1477-9226
dc.identifier.doi10.1039/c1dt00001b
dc.identifier.urihttp://hdl.handle.net/10072/42678
dc.description.abstractThe aquation profiles of two novel dinuclear polyamine-linked, platinum-based antitumour complexes [{trans-PtCl(15NH3)2}2{μ-(15NH2(CH2)615NH2(CH2)615NH2)}]3+ (BBR3007, 1,1/t,t-6,6, 1) and [{trans-PtCl(15NH3)2}2{μ-(15NH2(CH2)615NH2(CH2)215NH2(CH2)615NH2)}]4+ (BBR3610, 1,1/t,t-6,2,6, 1′) have been probed using 2D [1H, 15N] HSQC NMR spectroscopy. Reported herein are the rate constants for the hydrolysis of 1 and 1′, as well as the acid dissociation constants of the coordinated aqua ligands in their aquated derivatives. The aquation and anation rate constants for the single step aquation model in 15 mM NaClO4 (pH 5.4) at 298 K are, for 1, k1 = 7.2 ± 0.1 ×10−5s−1, k−1 = 0.096 ± 0.002 M−1s−1 and, for 1′, k1 = 4.0 ± 0.2 × 10−5s−1, k−1 = 1.4 ± 0.1 M−1s−1. The effect of the linker backbone (Pt(tetra(m)mine vs.polyamine) was evaluated by comparison with previous data for the trinuclear complex [{trans-PtCl(NH3)2}2(μ-trans-Pt(NH3)2{NH2(CH2)6NH2}2)]4+ (1,0,1/t,t,t or BBR3464). The pK1 for 1,0,1/t,t,t (3.44) is closest to that of 1 (3.12), while the pronounced difference for 1′ (4.54), means that 1′ is the least aquated of the three complexes at equilibrium. pKa values of 5.92 were calculated for the aquated forms of both 1 and 1′, which are 0.3 pK units higher than for either 1,0,1/t,t,t, or the dinuclear 1,1/t,t. The higher pKa values for both polyamine-linked compounds may be attributed to the formation of macrochelates between the central NH2 groups and the {PtN3O} coordination sphere of the aquated species.
dc.description.peerreviewedYes
dc.description.publicationstatusYes
dc.languageEnglish
dc.language.isoeng
dc.publisherRoyal Society of Chemistry
dc.publisher.placeUnited Kingdom
dc.relation.ispartofstudentpublicationN
dc.relation.ispartofpagefrom4147
dc.relation.ispartofpageto4154
dc.relation.ispartofissue16
dc.relation.ispartofjournalDalton Transactions
dc.relation.ispartofvolume40
dc.relation.urihttp://purl.org/au-research/grants/ARC/DP1095383
dc.relation.grantIDDP1095383
dc.relation.fundersARC
dc.rights.retentionY
dc.subject.fieldofresearchInorganic chemistry
dc.subject.fieldofresearchBioinorganic chemistry
dc.subject.fieldofresearchTheoretical and computational chemistry
dc.subject.fieldofresearchOther chemical sciences
dc.subject.fieldofresearchcode3402
dc.subject.fieldofresearchcode340201
dc.subject.fieldofresearchcode3407
dc.subject.fieldofresearchcode3499
dc.titleSolution studies of dinuclear polyamine-linked platinum-based antitumour complexes
dc.typeJournal article
dc.type.descriptionC1 - Articles
dc.type.codeC - Journal Articles
gro.date.issued2011
gro.hasfulltextNo Full Text
gro.griffith.authorBerners-Price, Sue J.


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