Figure 3.
Mechanistic studies. (a) Proposed mechanism for the reactivity between EBXs and phenols under the influence of visible light. Thermochemistry evaluation was conducted at the M06/Lanl2dz level of theory with CPCM-described solvation in acetonitrile; CPCM: conductor-like polarizable continuum model. Time-dependent density functional theory (TD-DFT) calculations to model the lowest excited states of the EDA complex were conducted at the CAM-B3LYP/Lanl2dz/CPCM-MeCN level of theory. HOMO: highest occupied molecular orbital; LUMO: lowest unoccupied molecular orbital; f: predicted oscillator strength. λcalc: predicted maximum wavelength of absorption of the lowest excited state. (b) 13C-labeling experiment. (c) Experiment involving deuterated phenol. (d) Experiment involving vinylbenziodoxolone and sodium phenoxide. (e) Light-driven reaction between EBX 2a, diboronate ester, and pyridine to yield (iodoethynyl)benzene.
