Specific Chelate Tuning of the Substitution Kinetics of Platinum(II) Complexes in Aqueous Solution

Fekl, Ulrich; Eldik, Rudi van

doi:10.1002/(sici)1099-0682(199803)1998:3<389::aid-ejic389>3.0.co;2-q

Cited by 18 publications

(15 citation statements)

References 49 publications

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“…In the UV-vis absorption spectrum of (R/S)-(1-4)•2b-CD•2NO 3 , a strong band centered at 280 nm was observed and is assigned the π -π* transitions of the phen ligand. It has been previously shown that this band has a weak dependence on the nature of the Pt II coordination sphere, 11,26 and the UV-vis band correlates well with that of other Pt II (phen) complexes. 11,[26][27] As a corollary, this band will also have weak dependence on the host-guest environment at the other extremity of the molecule.…”

Section: Cd•2nosupporting

confidence: 54%

“…It has been previously shown that this band has a weak dependence on the nature of the Pt II coordination sphere, 11,26 and the UV-vis band correlates well with that of other Pt II (phen) complexes. 11,[26][27] As a corollary, this band will also have weak dependence on the host-guest environment at the other extremity of the molecule. A weak band is also observed at 357 nm and is assigned to a MLCT transition by comparison with the parent compound [Pt(phen)(py) 2 ] 2+ which has been previously reported.…”

Section: Cd•2nosupporting

confidence: 54%

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Supramolecular β-Cyclodextrin Adducts of Boron-Rich DNA Metallointercalators Containing Dicarba-closo-dodecaborane(12)

2013

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A chiral, isomeric series of novel boron-rich Pt(II) metallointercalators ([PtL2(phen)](NO3)2: L = (x)-(1,y-closo-carboran-1-yl)pyrid-z-ylmethanol: x = R, S; y = 7, 12; z = 3, 4) wre prepared and fully characterized. By means of variable-temperature NMR spectroscopy, different combinations of Δ-head-to-tail, head-to-head, and Λ-head-to-tail rotamers were identified, and the free energies of activation for Pt-N bond rotation were determined for the pyrid-4-yl complexes with ΔG(‡)307 = 16.1 ± 0.3 kcal mol(-1) and ΔG(‡)325 = 16.2 ± 0.5 kcal mol(-1) for the 1,7-carboranyl derivative and ΔG(‡)307 = 16.4 ± 0.5 kcal mol(-1) and ΔG(‡)325 = 16.2 ± 0.5 kcal mol(-1) for the 1,12-carboranyl derivative. The corresponding 2:1 host-guest β-cyclodextrin (β-CD) adducts ([PtL2(phen)·2β-CD](NO3)2) were also prepared and fully characterized by high resolution electrospray ionization mass spectrometry and 2D-(1)H{(11)B} nuclear Overhauser enhancement spectroscopy and rotating-frame Overhauser effect spectroscopy NMR experiments. The interaction of the novel supramolecular adducts with calf thymus DNA was investigated by means of linear dichroism, ultraviolet-visible spectroscopy, thermal denaturation, and isothermal titration calorimetry experiments which revealed a bimodal binding regime with DNA intercalation favored at low [drug]/[DNA] ratios, while at higher drug loading, surface aggregation was observed. Furthermore, the data were also consistent with some degree of dissociation of the β-CD host-guest adducts upon DNA binding. When we used a single binding-site model, interpreted as a weighted average of all of the possible equilibrium interactions, the compounds showed high affinity for ct-DNA with K(assoc) ranging from (1.3 ± 0.1) × 10(5) M(-1) to (5.7 ± 0.4) × 10(5) M(-1). In general, the overall DNA-binding behavior was enthalpically driven with a minor or unfavorable entropic component, which is consistent with the thermodynamics of an intercalation-dominated process. A higher degree of DNA intercalation was observed for the R-isomer in the pyrid-3-yl compounds, and the opposite trend was observed in the case of pyrid-4-yl derivatives.

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Section: Cd•2nosupporting

confidence: 54%

Section: Cd•2nosupporting

confidence: 54%

Supramolecular β-Cyclodextrin Adducts of Boron-Rich DNA Metallointercalators Containing Dicarba-closo-dodecaborane(12)

2013

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“…The internal Pd…Pd distance is 3.0001(11) Å. The structure is isomorphous with the Pt analog [28], Pt…Pt is 3.0837 (14) [10]. In the latter, the Pd-O bond distances of 2.0228(19) and 2.0195(19) Å are experimentally equivalent to those found for (2) as are the Pd-N distances.…”

Section: [Pd(phen)(μ-oh)] 2 [O 3 Scf 3 ] 2 ·2h 2 O (2)-mentioning

confidence: 99%

Palladium(II) complexes of 1,10-phenanthroline: Synthesis and X-ray crystal structure determination

Adrian¹,

Broker²,

Tiekink³

et al. 2008

Inorganica Chimica Acta

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Two palladium(II) complexes, [Pd(phen) , in acetonitrile and water, respectively. The structures of both complexes are based on a Pd(phen) 2+ metal core, with two acetonitrile molecules binding in a monodentate fashion in complex 1 and two hydroxo bridges holding together two cores to form a dimer in complex 2. Additionally, both complexes present a hydrogen bonded 3-D network involving the triflate anions in 1, and water and triflate anions in 2. Both complexes have been characterized by infrared and 1 H NMR spectroscopy and their crystal structures determined by Xray crystallography.

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“…Experimental data for this reaction were reported earlier by some groups [16][17][18] independently. However, both steps of the reaction are supposed to pass through a pentacoordinated trigonal-bipyramidal (TB) transition state (TS) whose geometry may bring a new insight into the reaction dynamics of square planar Pt complex where the entering and leaving ligands are not 0166 identical.…”

Section: Introductionmentioning

confidence: 99%

A detailed theoretical study of the interaction of thiourea with cis-diaqua(ethylenediamine) platinum(II)

Banerjee¹,

Sengupta

Mukherjee

2009

Journal of Molecular Structure: THEOCHEM

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Specific Chelate Tuning of the Substitution Kinetics of Platinum(II) Complexes in Aqueous Solution

Cited by 18 publications

References 49 publications

Supramolecular β-Cyclodextrin Adducts of Boron-Rich DNA Metallointercalators Containing Dicarba-closo-dodecaborane(12)

Supramolecular β-Cyclodextrin Adducts of Boron-Rich DNA Metallointercalators Containing Dicarba-closo-dodecaborane(12)

Palladium(II) complexes of 1,10-phenanthroline: Synthesis and X-ray crystal structure determination

A detailed theoretical study of the interaction of thiourea with cis-diaqua(ethylenediamine) platinum(II)

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