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Naji, M. |
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Motta, Antonella |
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Aletan, Dirar |
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Mohamed, Tarek |
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Ertürk, Emre |
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Taccardi, Nicola |
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Kononenko, Denys |
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Petrov, R. H. | Madrid |
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Alshaaer, Mazen | Brussels |
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Bih, L. |
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Casati, R. |
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Muller, Hermance |
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Kočí, Jan | Prague |
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Šuljagić, Marija |
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Kalteremidou, Kalliopi-Artemi | Brussels |
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Azam, Siraj |
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Ospanova, Alyiya |
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Blanpain, Bart |
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Ali, M. A. |
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Popa, V. |
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Rančić, M. |
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Ollier, Nadège |
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Azevedo, Nuno Monteiro |
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Landes, Michael |
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Rignanese, Gian-Marco |
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Shiddiky, Muhammad J. A.
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (12/12 displayed)
- 2020Electropolymerized porous polymer films on flexible indium tin oxide using trifunctional furan substituted benzene conjugated monomer for biosensingcitations
- 2019Naphthalene flanked diketopyrrolopyrrolecitations
- 2018Robust free-standing nano-thin SiC membranes enable direct photolithography for MEMS sensing applicationscitations
- 2018Graphene-oxide-loaded superparamagnetic iron oxide nanoparticles for ultrasensitive electrocatalytic detection of microRNAcitations
- 2017Self-assembly of polymeric micelles made of asymmetric polystyrene-b-polyacrylic acid-b-polyethylene oxide for the synthesis of mesoporous nickel ferritecitations
- 2016Cyano-Bridged Trimetallic Coordination Polymer Nanoparticles and Their Thermal Decomposition into Nanoporous Spinel Ferromagnetic Oxidescitations
- 2016Biosensing made easy with PEG-targeted bi-specific antibodiescitations
- 2015Conditions Favoring the Formation of Monomeric PtIII Derivatives in the Electrochemical Oxidation of trans-[PtII{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]citations
- 2013"Drill and fill" lithography for controlled fabrication of 3D platinum electrodescitations
- 2012Fabrication and characterization of gold nanohole electrode arrayscitations
- 2008Fabrication of disposable sensors for biomolecule detection using hydrazine electrocatalystcitations
- 2007Hydrazine-catalyzed ultrasensitive detection of DNA and proteinscitations
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article
Conditions Favoring the Formation of Monomeric PtIII Derivatives in the Electrochemical Oxidation of trans-[PtII{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]
Abstract
<p>Characterization of the anticancer active compound trans-[Pt<sup>II</sup>{(p-BrC<sub>6</sub>F<sub>4</sub>)NCH<sub>2</sub>CH<sub>2</sub>NEt<sub>2</sub>}Cl(py)] is described along with identification of electrochemical conditions that favor formation of a monomeric one-electron-oxidized Pt<sup>III</sup> derivative. The square-planar organoamidoplatinum(II) compound was synthesized through a carbon dioxide elimination reaction. Structural characterization by using single-crystal X-Ray diffraction reveals a trans configuration with respect to donor atoms of like charges. As Pt<sup>III</sup> intermediates have been implicated in the reactions of platinum anticancer agents, electrochemical conditions favoring the formation of one-electron-oxidized species were sought. Transient cyclic voltammetry at fast scan rates or steady-state rotating disc and microelectrode techniques in a range of molecular solvents and an ionic liquid confirm the existence of a well-defined, chemically and electrochemically reversible one-electron oxidation process that, under suitable conditions, generates a Pt<sup>III</sup> complex, which is proposed to be monomeric [Pt<sup>III</sup>{(p-BrC<sub>6</sub>F<sub>4</sub>)NCH<sub>2</sub>CH<sub>2</sub>NEt<sub>2</sub>}Cl(py)]<sup>+</sup>. Electron paramagnetic resonance spectra obtained from highly non-coordinating dichloromethane/([Bu<sub>4</sub>N][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>]) solutions, frozen to liquid nitrogen temperature immediately after bulk electrolysis in a glove box, support the Pt<sup>III</sup> assignment rather than formation of a Pt<sup>II</sup> cation radical. However, the voltammetric behavior is highly dependent on the timescale of the experiments, temperature, concentration of trans-[Pt<sup>II</sup>{(p-BrC<sub>6</sub>F<sub>4</sub>)NCH<sub>2</sub>CH<sub>2</sub>NEt<sub>2</sub>}- Cl(py)], and the solvent/electrolyte. In the low-polarity solvent CH<sub>2</sub>Cl<sub>2</sub> containing the very weakly coordinating electrolyte [Bu<sub>4</sub>N][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>], a well-defined reversible one-electron oxidation process is observed on relatively long timescales, which is consistent with the stabilization of the cationic platinum(III) complex in non-coordinating media. Bulk electrolysis of low concentrations of [Pt{(p-BrC<sub>6</sub>F<sub>4</sub>)NCH<sub>2</sub>CH<sub>2</sub>NEt<sub>2</sub>}Cl(py)] favors the formation of monomeric [Pt<sup>III</sup>{(p-BrC<sub>6</sub>F<sub>4</sub>)NCH<sub>2</sub>CH<sub>2</sub>NEt<sub>2</sub>}Cl(py)]<sup>+</sup>. Simulations allow the reversible potential of the Pt<sup>II</sup>/Pt<sup>III</sup> process and the diffusion coefficient of [Pt<sup>III</sup>{(p-BrC<sub>6</sub>F<sub>4</sub>)- NCH<sub>2</sub>CH<sub>2</sub>NEt<sub>2</sub>}Cl(py)]<sup>+</sup> to be calculated. Reversible electrochemical behavior, giving rise to monomeric platinum(III) derivatives, is rare in the field of platinum chemistry.</p>