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Electrochemical dehalogenation of polyhalogenated compounds is an inefficient process as the working electrode is passivated by the deposition of short-chain polymers that form during the early stages of electrolysis. Herein, we report the use of 1, 1, 1, 3, 3, 3-hexaflouroisopropanol (HFIP) as an efficient reagent to control C–H formation over the radical association. Debromination of 1,6-dibromohexane was examined in the presence of Ni(II) salen and HFIP as the electrocatalyst and hydrogen atom source, respectively. Electrolysis of 10 mM 1,6-dibromohexane and 2 mM Ni(II) salen in the absence of HFIP yields 50% unreacted 1,6-dibromohexane and ∼40% unaccounted for starting material, whereas electrolysis with 50 mM HFIP affords 65%n-hexane. The mechanism of hydrogen atom incorporation was examined via deuterium incorporation coupled with high-resolution mass spectrometry, and density functional theory (DFT) calculations. Deuterium incorporation analysis revealed that the hydrogen atom originated from the secondary carbon of HFIP. DFT calculations showed that the deprotonation of hydroxyl moiety of HFIP, prior to the hydrogen atom transfer, is a key step for C–H formation. The scope of electrochemical dehalogenation was examined by electrolysis of 10 halogenated compounds. Our results indicate that through the use of HFIP, the formation of short-chain polymers is no longer observed, and monomer formation is the dominant product.

Time‐dependent density functional theory (TDDFT) was applied to gain insights into the electronic and vibrational spectroscopic properties of an important electron transport mediator, methyl viologen (MV²⁺). An organic dication, MV²⁺has numerous applications in electrochemistry that include energy conversion and storage, environmental remediation, and chemical sensing and electrosynthesis. MV²⁺is easily reduced by a single electron transfer to form a radical cation species (MV^•+), which has an intense UV–visible absorption near 600 nm. The redox properties of the MV²⁺/MV^•+couple and light‐sensitivity of MV^•+have made the system appealing for photo‐electrochemical energy conversion (e.g., solar hydrogen generation from water) and the study of photo‐induced charge transfer processes through electronic absorption and resonance Raman spectroscopic measurements. The reported work applies leading TDDFT approaches to investigate the electronic and vibrational spectroscopic properties of MV²⁺and MV^•+. Using a conventional hybrid exchange functional (B3‐LYP) and a long‐range corrected hybrid exchange functional (ωB97X‐D3), including with a conductor‐like polarizable continuum model to account for solvation, the electronic absorption and resonance Raman spectra predicted are in good agreement with experiment. Also analyzed are the charge transfer character and natural transition orbitals derived from the TDDFT vertical excitations calculated. The findings and models developed further the understanding of the electronic properties of viologens and related organic redox mediators important in renewable energy applications and serve as a reference for guiding the interpretation of electronic absorption and Raman spectra of the ions.