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Conditions favoring the formation of monomeric Pt(III) derivatives in the electrochemical oxidation of trans-[Pt(II){(p-BrC6F4)NCH2CH2NEt2}Cl(py)]

Ojha, Ruchika, Nafady, Ayman, Shiddiky, M. J. A., Mason, Dayna, Boas, John F., Torriero, Angel A. J., Bond, Alan M., Deacon, Glen B. and Junk, Peter C. 2015, Conditions favoring the formation of monomeric Pt(III) derivatives in the electrochemical oxidation of trans-[Pt(II){(p-BrC6F4)NCH2CH2NEt2}Cl(py)], ChemElectroChem, vol. 2, no. 7, pp. 1048-1061, doi: 10.1002/celc.201402447.

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Title Conditions favoring the formation of monomeric Pt(III) derivatives in the electrochemical oxidation of trans-[Pt(II){(p-BrC6F4)NCH2CH2NEt2}Cl(py)]
Author(s) Ojha, Ruchika
Nafady, Ayman
Shiddiky, M. J. A.
Mason, Dayna
Boas, John F.
Torriero, Angel A. J.ORCID iD for Torriero, Angel A. J. orcid.org/0000-0001-8616-365X
Bond, Alan M.
Deacon, Glen B.
Junk, Peter C.
Journal name ChemElectroChem
Volume number 2
Issue number 7
Start page 1048
End page 1061
Total pages 14
Publisher Wiley
Place of publication Weinheim, Germany
Publication date 2015-07-15
ISSN 2196-0216
Keyword(s) Anticancer compounds
EPR spectroscopy
Oxidation
Simulations
Voltammetry
Summary Characterization of the anticancer active compound trans-[PtII{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] is described along with identification of electrochemical conditions that favor formation of a monomeric one-electron-oxidized PtIII 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 PtIII 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 PtIII complex, which is proposed to be monomeric [PtIII{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]+. Electron paramagnetic resonance spectra obtained from highly non-coordinating dichloromethane/([Bu4N][B(C6F5)4]) solutions, frozen to liquid nitrogen temperature immediately after bulk electrolysis in a glove box, support the PtIII assignment rather than formation of a PtII cation radical. However, the voltammetric behavior is highly dependent on the timescale of the experiments, temperature, concentration of trans-[PtII{(p-BrC6F4)NCH2CH2NEt2}- Cl(py)], and the solvent/electrolyte. In the low-polarity solvent CH2Cl2 containing the very weakly coordinating electrolyte [Bu4N][B(C6F5)4], 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-BrC6F4)NCH2CH2NEt2}Cl(py)] favors the formation of monomeric [PtIII{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]+. Simulations allow the reversible potential of the PtII/PtIII process and the diffusion coefficient of [PtIII{(p-BrC6F4)- NCH2CH2NEt2}Cl(py)]+ to be calculated. Reversible electrochemical behavior, giving rise to monomeric platinum(III) derivatives, is rare in the field of platinum chemistry.
Language eng
DOI 10.1002/celc.201402447
Field of Research 030604
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
Copyright notice ©2015, Wiley
Persistent URL http://hdl.handle.net/10536/DRO/DU:30077026

Document type: Journal Article
Collection: School of Life and Environmental Sciences
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