Solvents Promote Selective TEDA 2+. Formation Driven through a Pnicogen Bond in Selectfluor

We report the first evidence of TEDA 2+ radical formation from Selectfluor in electron-rich solvents. Electron paramagnetic resonance (EPR) experiments demonstrated the spontaneous formation of radical species from Selectfluor solutions in DMF, acetonitrile, and acetone. From 19 F NMR, association constants of 0.2163, 0.0151, and 0.0095 M –1 were determined for Selectfluor solutions in DMF, acetonitrile, and acetone, respectively. DFT calculations identified a pnicogen bond between the N-F nitrogen of Selectfluor and solvent. This interaction is proposed as an initial step for the formation of the TEDA 2+ radical.