Oxo-Mn(V) porphyrin complexes perform competitive hydroxylation, desaturation, and radical rearrangement reactions using diagnostic substrate norcarane. Initial C-H cleavage proceeds through the two hydrogen abstraction steps from the two adjacent carbon on the norcarane and then through selective reactions various products are generated. Using density functional theory calculations, we show that the hydroxylation and desaturation reactions are triggered by a rate-determining H-abstraction step, whereas the rate-determining step for the radical rearrangement is located at the rebound step (TS2). We find that the endo-2 reaction is favorable over other reactions, which is consistent with the experimental result. Furthermore, the competitive pathways for norcarane oxidation depend on the non-covalent interaction between norcarane and the porphyrin-ring, and orbital energy gaps between donor and acceptor orbitals because of stable or unstable acceptor orbital. The stereo- and regio-selectivities of norcarane oxidation are hardly sensitive to the zero-point energy and thermal free energy corrections.
Keywords: density functional calculations; electronic structure; hydroxylation and desaturation reactions; non-covalent interactions; oxo-manganese(V) complex.
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