Scheme 3. Unusual Spin Density Flow Observed in the DFT-Computed Electronically Asynchronous Transition States for C–N Bond Formation, Graphical Representations and Spin Densities (α–β) for TS4 (A), TS4^NH3 (B), TS2 (C), and TS2′ (D).

Blue bars describe cobalt-centered orbitals. Blue, red, and green lobes represent empty, 1e^– filled and 2e^– filled TAML-, and nitrene-based orbitals. Yellow lobes in the graphical representations indicate α-spin density, and blue lobes indicate β-spin density. H atoms (except for vinylic protons) are omitted for clarity.