N,N'-diaryl-sulfurdiimides are strongly redox tuned
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Date
2024
Authors
Hill, Nathan D. D.
Boeré, René T.
Journal Title
Journal ISSN
Volume Title
Publisher
Wiley
Abstract
The synthesis and extensive characterization of nine aryl sulfur diimides (SDIs, Ar−NSN−Ar) are presented with a robust computational and experimental investigation of the fundamental properties of these important members of the thiazyl family of compounds, with particular attention paid to their highly tunable electrochemical behaviour. This is the first work to undertake a systematic comparison of the electrochemical profiles of a coherent series of SDIs to demonstrate and quantify the response of their reduction potentials to substituent electron-donating and -withdrawing properties. This effect is found to be not only exceptionally strong, but also correlates very closely with computed orbital energies. Electron paramagnetic resonance spectroscopy is used to determine the nature, localization, and qualitative lifetimes of the radical anions of SDIs. This work also addresses significant misconceptions about physical properties of SDIs. Experimental data and modern computational methods are employed to provide a resolute answer to the long-standing contention of the solution-state conformations of SDIs, and to correct historical mistakes in the assignment of infrared spectroscopic data. High-quality crystal structures of all SDIs in this work showcase the utility of the recently introduced structural refinement software NoSpherA2, enabling full anisotropic refinement of H-atoms with accurate C−H bond lengths.
Description
Open access article. Creative Commons Attribution 4.0 International license (CC BY 4.0 DEED) applies
Keywords
Thiazyl chemistry , Electrochemistry , Chemical synthesis , EPR spectroelectrochemistry , DFT computation , SC-XRD structure determination , Infrared spectroscopy , UV-vis spectroscopy
Citation
Hill, N. D. D., & Boeré, R. T. (2024). N,N'-diaryl-sulfurdiimides are strongly redox tuned. Chemistry-A European Journal,30(26), Article e202400563. https://doi.org/10.1002/chem.202400563