Modulation of Biorelevant Radical Reactions by Non‐covalent Interactions

Revealing the nature of covalently tethered distonic radical anions in the generation of heteroatom-centered radicals: evidence for the polarity-matching PCET pathway

“…For a better comprehension of differences in reactivity and properties between dicarboxylic radical anions and acyloxy radicals, it is important to understand the inuence of the presence of COO − A + (A = TBA or Cs) on the modulation of the BDEs of the acyloxy O-X (X = Br, I), which in turn affects the stability of the acyl hypohalites or the acyloxy radical (Section S7.5 †). 38 It is found that the BDE of the O-Br bond in BCTC-1 (BDE Pc = 29.3 kcal mol −1 ) is much lower than that of acyl hypobromite substituted by COOH or without substitution (BDE Pb = 36.4 kcal mol −1 and BDE Pa = 35.5 kcal mol −1 ), implying that the presence of COO − A + is critical for the stability of the resulting TDRAs (Fig. 3c and S37, S38 †).…”