Fig. 6: DFT calculations.
From: Ni-catalyzed benzylic β-C(sp3)–H bond activation of formamides
The computations were performed at the B3LYP-D3(BJ)/def2- TZVPP-SMD(toluene)//B3LYP-D3(BJ)/def2-SVP level of theory. a Comparison between oxidative addition and ligand-to-ligand H transfer for formyl C–H bond activation, and the result shows that the latter is a preferred pathway. b Product-forming pathway via 4-membered nickelacycle. c Calculation on the activation Gibbs energy of γ-C(sp3)–H bond of TP group, indicating 17.1 kcal/mol (TS-iso), which is a little higher than the activation Gibbs energy of benzylic β-C(sp3)–H bond (15.6 kcal/mol, TS3).
