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Systematic reaction path exploration revealed the entire mechanism of Knowles's light‐promoted catalytic intramolecular hydroamination. Bond formation/cleavage competes with single electron transfer (SET) between the catalyst and substrate. These processes are described by adiabatic processes through transition states in an electronic state and non‐radiative transitions through the seam of crossings (SX) between different electronic states. This study determined the energetically favorable SET path by introducing a practical computational model representing SET as non‐adiabatic transitions via SXs between substrate's potential energy surfaces for different charge states adjusted based on the catalyst's redox potential. Calculations showed that the reduction and proton shuttle process proceeded concertedly. Also, the relative importance of SET paths (giving the product and leading back to the reactant) varies depending on the catalyst's redox potential, affecting the yield. [ABSTRACT FROM AUTHOR]

Keywords: Computational Chemistry; Hydroamination; Photoredox Catalysis; Radical Reactions; Reaction Networks EN Computational Chemistry Hydroamination Photoredox Catalysis Radical Reactions Reaction Networks 1 1 1 01/02/23 20230102 NES 230102 B Systematic reaction path exploration b revealed the entire mechanism of Knowles' light-promoted catalytic intramolecular hydroamination via radical processes. In their Research Article (e202211936), Yu Harabuchi, Satoshi Maeda, and co-workers investigated the energetically favorable reaction path by constructing reaction path networks and searching for the seam of crossing geometries. In their Research Article (e202211936), Yu Harabuchi, Satoshi Maeda, and co-workers investigated the energetically favorable reaction path by constructing reaction path networks and searching for the seam of crossing geometries. [Extracted from the article]

In their Research Article (e202211936), Yu Harabuchi, Satoshi Maeda, and co-workers investigated the energetically favorable reaction path by constructing reaction path networks and searching for the seam of crossing geometries. In their Research Article (e202211936), Yu Harabuchi, Satoshi Maeda, and co-workers investigated the energetically favorable reaction path by constructing reaction path networks and searching for the seam of crossing geometries. Keywords: Computational Chemistry; Hydroamination; Photoredox Catalysis; Radical Reactions; Reaction Networks EN Computational Chemistry Hydroamination Photoredox Catalysis Radical Reactions Reaction Networks 1 1 1 01/02/23 20230102 NES 230102 B Systematic reaction path exploration b revealed the entire mechanism of Knowles' light-promoted catalytic intramolecular hydroamination via radical processes. [Extracted from the article]

Systematic reaction path exploration revealed the entire mechanism of Knowles's light‐promoted catalytic intramolecular hydroamination. Bond formation/cleavage competes with single electron transfer (SET) between the catalyst and substrate. These processes are described by adiabatic processes through transition states in an electronic state and non‐radiative transitions through the seam of crossings (SX) between different electronic states. This study determined the energetically favorable SET path by introducing a practical computational model representing SET as non‐adiabatic transitions via SXs between substrate's potential energy surfaces for different charge states adjusted based on the catalyst's redox potential. Calculations showed that the reduction and proton shuttle process proceeded concertedly. Also, the relative importance of SET paths (giving the product and leading back to the reactant) varies depending on the catalyst's redox potential, affecting the yield. [ABSTRACT FROM AUTHOR]