Theoretical Exploration of Energy Transfer and Single Electron Transfer Mechanisms to Understand the Generation of Triplet Nitrene and the C(sp(3))–H Amidation with Photocatalysts

[Image: see text] Mechanistic explorations and kinetic evaluations were performed based on electronic structure calculations at the CASPT2//CASSCF level of theory, the Fermi’s golden rule combined with the Dexter model, and the Marcus theory to unveil the key factors regulating the processes of photocatalytic C(sp(3))–H amidation starting from the newly emerged nitrene precursor of hydroxamates. The highly reactive nitrene was found to be generated efficiently via a triplet–triplet energy transfer process and to be benefited from the advantages of hydroxamates with long-range charge-transfer (CT) excitation from the N-centered lone pair to the 3,5-bis(trifluoromethyl)benzoyl group. The properties of the metal-to-ligand charge-transfer (MLCT) state of photocatalysts, the functionalization of chemical moieties for substrates involved in the charge-transfer (CT) excitation, such as the electron-withdrawing trifluoromethyl group, and the energetic levels of singlet and triplet reaction pathways may regulate the reaction yield of C(sp(3))–H amidation. Kinetic evaluations show that the triplet–triplet energy transfer is the main driving force of the reaction rather than the single electron transfer process. The effects of electronic coupling, molecular rigidity, and excitation energies on the energy transfer efficiency were further discussed. Finally, we investigated the inverted behavior of single-electron transfer, which is correlated unfavorably to the catalytic efficiency and amidation reaction. All theoretical explorations allow us to better understand the generation of nitrene with visible-light photocatalysts, to expand highly efficient substrate sources, and to broaden our scope of available photosensitizers for various cross-coupling reactions and the construction of N-heterocycles.