The first structural models of the proposed cis-Fe III (OH)(halide) intermediate in the non-heme iron halogenases were synthesized and examined for their inherent reactivity with tertiary carbon radicals. Selective hydroxylation occurs for these cis-Fe III (OH)(X) (X = Cl, Br) complexes in a radical rebound-like process. In contrast, a cis-Fe III (Cl) 2 complex reacts with carbon radicals to give halogenation. These results are discussed in terms of the inherent reactivity of the analogous rebound intermediate in both enzymes and related catalysts.
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