Increasing the steric hindrance around the catalytic core of a self-assembled imine-based non-heme iron catalyst for C-H oxidation.

Sterically hindered imine-based non-heme complexes 4 and 5 rapidly self-assemble in acetonitrile at 25 °C, when the corresponding building blocks are added in solution in the proper ratios. Such complexes are investigated as catalysts for the H 2 O 2 oxidation of a series of substrates in order to ascertain the role and the importance of the ligand steric hindrance on the action of the catalytic core 1, previously shown to be an efficient catalyst for aliphatic and aromatic C-H bond oxidation. The study reveals a modest dependence of the output of the oxidation reactions on the presence of bulky substituents in the backbone of the catalyst, both in terms of activity and selectivity. This result supports a previously hypothesized catalytic mechanism, which is based on the hemi-lability of the metal complex. In the active form of the catalyst, one of the pyridine arms temporarily leaves the iron centre, freeing up a lot of room for the access of the substrate.