Fig. 5: Mechanistic investigations.
a, Stern–Volmer plot of in situ generated I+BF4– luminescence quenching by TBACl, TBANO3 and 1-dodecene. I0, luminescence intensity without quencher; I, luminescence intensity with quencher. b, Radical trapping experiments with 1,1-dichloro-2-vinylcyclopropane. Reaction conditions for hydrochlorination: alkene (1.0 mmol), HCl(aq. 37%) (1.5 mmol), 1 (10 mol%), bis(4-methoxyphenyl) disulfide (10 mol%) in fluorobenzene/acetone (10 ml, 5:1 v/v) at 29 °C under 40 W blue LED for 48 h. Reaction conditions for hydronitrooxylation: alkene (1.0 mmol), HNO3(aq. 65%) (3.0 mmol), 1 (10 mol%), 2,4,6-triisopropylthiophenol (TRIPSH, 15 mol%) in acetone/H2O/diethyl ether (13 ml, 10:2:1 v/v/v) at 29 °C under 40 W blue LED for 48 h. See Supplementary Methods for the detailed experimental procedure. c, DFT-calculated energy profiles (kcal mol–1) for the reaction of Cl· with 1-butene. d, DFT-calculated energy profiles (kcal mol–1) for the reaction of NO3· with 1-butene. e, DFT-calculated energy profiles (kcal mol–1) for the reaction of carbon-centred radical intermediates (Intlinear and Intbranched) and 4-methoxythiophenol (RSH). f, DFT-calculated energy profiles (kcal mol–1) for the reaction of carbon-centred radical intermediates (Intlinear,nit and Intbranched,nit) and pentafluorothiophenol (R′SH).
