Figure 2.

Reaction coordinate of nitrene transfer from B(N) to 1 to give either the C‒H amination (brown) or aziridine product (brown). R = reactant, TS = transition state, Int = intermediate, and PC = product complex. Subscript I = C‒H insertion and A = aziridination; superscript OS1 and 3 denote open-shell singlet and triplet spin states, respectively. Solid lines denote the triplet PES, and dashed lines denote the open-shell singlet PES. Arrows and the size of the arrows represent α or β spin populations for the electrons on Ag (silver), N (brown), and organic substrate (black). Black arrows inside the ring indicate that electron density is delocalized over the allylic radical and arrows outside the ring represent electron density localized on the carbon proximal to the arrow. Numbers shown are Gibbs free energies; numbers enclosed in parentheses are enthalpies, both taking into account the solvent (CH₂Cl₂). Note: the energy for the blue dashed line enclosed by quotation marks was obtained from converging the single point energy at the OS singlet state based on the geometry of the solid blue line below it.