Accelerating the Photocatalytic Atom Transfer Radical Addition Reaction Induced by Bi ₂ O ₃ with Amines: Experiment and Computation

Metal oxide semiconductors are widely used in photocatalysis for the sustainable synthesis of fine chemicals and fuels. However, mechanisms actual catalytically active species involved these photocatalytic processes not yet fully understood. Herein, we reveal that addition certain amines can effectively accelerate atom transfer radical (ATRA) reaction by stabilizing a soluble Bi-species formed through between Bi2O3 diethyl bromomalonate using either N, N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) as solvent. Moreover, thermodynamic calculations revealed N’, N’-tetramethylethylenediamine (TMEDA), DMF yield most stable complexes [(κ2-TMEDA)2BiBr3], ultimately accelerating formation targeted ATRA product.