The mimicry of enzymatic catalysis with artificial systems has been a long standing goal of synthetic supramolecular chemistry. It is now widely accepted that, in order to rival the proficiency of enzymes, an artificial system must be built so that it defines a confined space where the substrate is isolated from bulk medium and exposed to direct contact with appropriate functional groups, a distinct feature of proteins and enzymes. Following this idea, we have developed a deep cavitand receptor (1) functionalized with a bis(pyridyl)dipyrrolidine tetradentate ligand. Binding of divalent metal ions (M2+ = Mn2+, Fe2+ and Zn2+) at the tetradentate ligand results in the formation of cavitand complexes 1●M(OTf)2. The complexes 1●M(OTf)2 (M = Fe(II) and Mn(II)) catalyze selective hydroxylation of aliphatic C-H bonds and epoxidation of olefins with hydrogen peroxide, exhibiting selectivity patterns consistent with the implication of high valent metal-oxo species. Furthermore, 1●Fe(OTf)2 reacts with IO4- to form an oxoiron(IV) complex [1●Fe(O)]2+, without decomposition of the supramolecular container.

Deep cavitand receptor functionalized with Fe(II) and Mn(II) aminopyridine complexes for bioinspired oxidation catalysis

256th National Meeting (2018)

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