Differences in and Comparison of the Catalytic Properties of Heme and Non‐Heme Enzymes with a Central Oxo–Iron Group

Why so aggressive? Density functional calculations on the oxo–iron active species of dioxygenase and monooxygenase enzyme models show that the former ones are more aggressive catalysts with low reaction barriers. The differences are assigned to electronic factors, such as the electron transfer into a σ* anti-bonding FeO orbital and the reduction of the metal to an FeIII center in the rate-determining step.