Abstract
• Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations for the photo carboxylation of the benzylic C( sp 3 )-H bond catalyzed by xanthone/nickel. • This study corroborates the previous proposal that light promotes the H-transfer from benzylic C( sp 3 )-H bond of the p -methoxytoluene to excited state of photocatalyst xanthone. • Ni(0) catalyst could mediate the H-transfer to occur via an electron-coupled-proton transfer manner, and then remarkably facilitates the carboxylation step. • The generated Ni(I) intermediate and ketyl radical anion complete the carboxylation and electron transfer processes independently. The photo carboxylation of the benzylic C( sp 3 )-H bond catalyzed by xanthone/nickel were examined by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. This study corroborates the previous proposal that light promotes the H-transfer from benzylic C( sp 3 )-H bond of the p -methoxytoluene to excited state of photocatalyst xanthone. Meanwhile, Ni(0) catalyst could mediate the H-transfer to occur via an electron-coupled-proton transfer manner, and then remarkably facilitates the carboxylation step (compared to the Ni-absent systems). After that, the generated Ni(I) intermediate and ketyl radical anion complete the carboxylation and electron transfer processes independently.
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