Manganese triazacyclononane oxidation catalysts grafted under reaction conditions on solid cocatalytic supports.

Manganese complexes of 1,4,7-trimethyl-1,4,7-triazacyclononane (tmtacn) are highly active and selective alkene oxidation catalysts with aqueous H(2)O(2). Here, carboxylic acid-functionalized SiO(2) simultaneously immobilizes and activates these complexes under oxidation reaction conditions. H(2)O(2) and the functionalized support are both necessary to transform the inactive [(tmtacn)Mn(IV)(μ-O)(3)Mn(IV)(tmtacn)](2+) into the active, dicarboxylate-bridged [(tmtacn)Mn(III)(μ-O)(μ-RCOO)(2)Mn(III)(tmtacn)](2+).

A heterogeneous, selective oxidation catalyst based on Mn triazacyclononane grafted under reaction conditions.

A unique method has been developed to synthesize an active heterogeneous oxidation catalyst by the in situ grafting of a 1,4,7-trimethyl-1,4,7-triazacyclononane manganese complex on carboxylic acid-functionalized supports serving dual roles as surface tether and necessary co-catalyst, massively increasing total turnovers as compared to the homogeneous analog.