Direct Observation of Oxygen Rebound with an Iron-Hydroxide Complex

The
rebound mechanism for alkane hydroxylation was invoked over
40 years ago to help explain reactivity patterns in cytochrome P450,
and subsequently has been used to provide insight into a range of
biological and synthetic systems. Efforts to model the rebound reaction
in a synthetic system have been unsuccessful, in part because of the
challenge in preparing a suitable metal-hydroxide complex at the correct
oxidation level. Herein we report the synthesis of such a complex.
The reaction of this species with a series of substituted radicals
allows for the direct interrogation of the rebound process, providing
insight into this uniformly invoked, but previously unobserved process.