Nucleophilic reactivity of a series of peroxomanganese(III) complexes supported by tetradentate aminopyridyl ligands

Peroxomanganese(III) adducts have been postulated as important intermediates in manganese-containing enzymes and small molecule oxidation catalysts. Synthetic peroxomanganese(III) complexes are known to be nucleophilic and facilitate aldehyde deformylation, offering a convenient way to compare relative reactivities of complexes supported by different ligands. In this work, tetradentate dipyridyldiazacycloalkane ligands with systematically perturbed steric and electronic properties were used to generate a series of manganese(II) and peroxomanganese(III) complexes. X-Ray crystal structures of five manganese(II) complexes all show the ligands bound to give trans complexes. Treatment of these Mn-II precursors with H2O2 and Et3N in MeCN at -40 degrees C results in the formation of peroxomanganese(III) complexes that differ only in the identity of the pyridine ring substituent and/or the number of carbons in the diazacycloalkane backbone. To determine the effects of small ligand perturbations on the reactivity of the peroxo group, the more thermally stable peroxomanganese(III) complexes were reacted with cyclohexanecarboxaldehyde. For these complexes, the rate of deformylation does not correlate with the expected nucleophilicity of the peroxomanganese(III) unit, as the inclusion of methyl substituents on the pyridines affords slower deformylation rates. It is proposed that adding methyl-substituents to the pyridines, or increasing the number of carbons on the diazacycloalkane, sterically hinders nucleophilic attack of the peroxo ligand on the carbonyl carbon of the aldehyde.