Electron delocalization in spectroelectrochemically and computationally characterized [Pt{(p-BrC6F4)NCH═C(Cl)NEt2}Cl(py)]+ formed by electrochemical oxidation of [PtII{(p-BrC6F4)NCH═C(Cl)NEt2}Cl(py)]

[Pt{(p-BrC₆F₄)NCH═C(Cl)NEt₂}Cl(py)] (1Cl) is the product of the hydrogen peroxide oxidation of the Pt^II anticancer agent [Pt{(p-BrC₆F₄)NCH₂CH₂NEt₂}Cl(py)] (1). Insights into electron delocalization and bonding in [Pt{(p-BrC₆F₄)NCH═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 oxidation of 1Cl to 1Cl⁺ and the reduction of 1Cl⁺ back to 1Cl confirm the long-term chemical reversibility. DFT calculations indicate only a minor contribution to the electron density (13%) resides on the Pt metal center in 1Cl⁺, indicating that the 1Cl/1Cl⁺ oxidation process is extensively ligand-based. Published X-ray crystallographic data show that 1Cl is present in only one structural form, while NMR data on the dissolved crystals revealed the presence of two closely related structural forms in an almost equimolar ratio. Solution-phase EPR spectra of 1Cl⁺ are consistent with two closely related structural forms in a ratio of about 90:10. The average g value for the frozen solution spectra (2.0567 for the major species) is significantly greater than the 2.0023 expected for a free radical. Crystal field analysis of the EPR spectra leads to an estimate of the 5d(xz) character of around 10% in 1Cl⁺. Analysis of X-ray absorption fine structure derived from 1Cl⁺ also supports the presence of a delocalized singly occupied metal molecular orbital with a spin density of approximately 17% on Pt. Accordingly, the considerably larger electron density distribution on the ligand framework (diminished Pt^III character) is proposed to contribute to the increased stability of 1Cl⁺ compared to that of 1⁺.