Abstract
Metal-peroxo intermediates are key species in the
catalytic cycles of nonheme metalloenzymes, but their chemical
properties and reactivity patterns are still poorly understood. We
report here the synthesis and characterization of a manganese(III)-
peroxo complex with a pentadentate bispidine ligand system and
studied its reactivity with aldehydes. We show that manganese(III)-
peroxo can react through hydrogen atom abstraction reactions
instead of the commonly proposed nucleophilic addition reaction.
Evidence of the mechanism comes from experiments which identify
a primary kinetic isotope effect of 5.4 for the deformylation reaction.
Computational modelling supports the established mechanism and
identifies the origin of the reactivity preference of hydrogen atom
abstraction over nucleophilic addition.
catalytic cycles of nonheme metalloenzymes, but their chemical
properties and reactivity patterns are still poorly understood. We
report here the synthesis and characterization of a manganese(III)-
peroxo complex with a pentadentate bispidine ligand system and
studied its reactivity with aldehydes. We show that manganese(III)-
peroxo can react through hydrogen atom abstraction reactions
instead of the commonly proposed nucleophilic addition reaction.
Evidence of the mechanism comes from experiments which identify
a primary kinetic isotope effect of 5.4 for the deformylation reaction.
Computational modelling supports the established mechanism and
identifies the origin of the reactivity preference of hydrogen atom
abstraction over nucleophilic addition.
| Original language | English |
|---|---|
| Pages (from-to) | 11257‒11261 |
| Number of pages | 5 |
| Journal | Angewandte Chemie (International Edition) |
| Volume | 55 |
| Issue number | 37 |
| Early online date | 8 Jul 2016 |
| DOIs | |
| Publication status | Published - 1 Sept 2016 |