Fig. 6: Mechanistic insights into EDA-initiated radical anion propagation.
From: Anti-Friedel–Crafts alkylation via electron donor–acceptor photoinitiation
a,b, Experimental kinetic studies monitored by 1H NMR spectroscopy. Standard kinetic conditions: RAE (1) = 0.15 M, 1 equiv.; phthalonitrile = 3 equiv.; DABCO = 1 equiv.; 450 nm LED; DMSO. The reported data correspond to mean conversions from three kinetic runs with standard deviations. KPhtl, potassium phthalimide; KPhtl-Cl, potassium tert-chlorophthalimide; Phtl-H, phthalimide; Std., standard conditions. c,d, Simulated time and concentration profiles via microkinetic modelling using DFT-computed Gibbs energies (Supplementary Fig. 6.7.1 and Supplementary Table 6.7.2) under standard kinetic conditions (c) and under standard kinetic conditions with the addition of KPhtl (d) (0.2 equiv.). e, Characterization of the EDA complex via UV–vis spectra: RAE (1) = 0.15 M, 1 equiv.; DABCO = 0.5 equiv.; phthalonitrile = 3 equiv.; Cs2CO3 = 0.05 equiv.; DMSO; path length = 1 mm. The vertical line at 450 nm represents the irradiative wavelength of the blue LED. Inset: Job plot with absorbance at 450 nm (Supplementary Section 7.3). f, Cyclic voltammograms (100 mV s−1) of phthalonitrile (10 mM), 4-(1-methylcyclohexyl)phthalonitrile (2, 10 mM), methylcyclohexyl RAE (1, 10 mM) and [nBu4N]+[PF6]− (100 mM) in DMSO under N2 in contact with a glassy-carbon-disc working electrode (0.071 cm2) with potential normalized to the ferrocene (Fc/Fc+) redox couple. MKM, microkinetic modelling.
