Journal article
Electron Delocalization in Spectroelectrochemically and Computationally Characterized [Pt{(p-BrC6F4)NCHâ• C(Cl)NEt2}Cl(py)] Formed by Electrochemical Oxidation of [PtII{(p-BrC6F4)NCHâ• C(Cl)NEt2}Cl(py)]
R Ojha, JF Boas, SP Best, AJ Canty, PC Junk, GB Deacon, AM Bond
Inorganic Chemistry | Published : 2021
Abstract
[Pt{(p-BrC6F4)NCHâ• C(Cl)NEt2}Cl(py)] (1Cl) is the product of the hydrogen peroxide oxidation of the PtII anticancer agent [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] (1). Insights into electron delocalization and bonding in [Pt{(p-BrC6F4)NCHâ• C(Cl)NEt2}Cl(py)]+ (1Cl+) obtained by electrochemical oxidation of 1Cl have been gained by spectroscopic and computational studies. The 1Cl/1Cl+ process is chemically and electrochemically reversible on the short time scale of voltammetry in dichloromethane (0.10 M [Bu4N][PF6]). Substantial stability is retained on longer time scales enabling a high yield of 1Cl+ to be generated by bulk electrolysis. In situ IR and visible spectroelectrochemical studies on the ..
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Awarded by Australian Research Council
Funding Acknowledgements
A.M.B. gratefully acknowledges financial support from the Australian Research Council. R.O. thanks the Australian Government for the provision of an Australian Postgraduate Award. The ARC is thanked for funding the purchase of the EPR instrument (LE0775660). X-ray spectroscopy was performed using the XAS beamline at the Australian Synchrotron, Victoria, Australia, part of ANSTO, and DFT computation was enabled by access to the National Computing Infrastructure. The authors thank the beamline team and, in particular, Dr. B. Johannessen for assistance during those experiments. The authors gratefully acknowledge Dr. Shashank Vittal Rao and Assoc. Prof. Alessandro Soncini (University of Melbourne) for helpful discussions and for investigating ab initio calculations of the EPR spectra.