Abstract
AbstractThe Marcus “Inverted Region” is found for back electron transfer reactions within geminate radical pairs consisting of triplet‐thionine and several aromatic donors. Measurements were performed in buffered methanol (pH = 8.6) at 295 K. The standard free energy change ΔG−et0 ranges from –54.0 to –150.5 kJ/mol by varying the donors from N,N,N′,N′‐tetramethyl‐p‐phenylendiamine, p‐phenylendiamine, p‐aminodiphenylamine, 1‐naphthylamine, diphenylamine, 9,10‐dimethylanthracene, 1,2,4‐trimethoxybenzene to 9‐methylanthracene. The rate constants start at 3.3 · 107 s−1, reach a maximum at 1.0 · 109 s−1 for 1‐naphthylamine and decrease to 1.7 · 108 s−1 for highly exergonic reactions.
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