The first structural models of the proposed cis-FeIII(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-FeIII(OH)(X) (X = Cl, Br) complexes in a radical rebound-like process. In contrast, a cis-FeIII(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.
The first structural models of the proposed cis-FeIII(OH)(n class="Chemical">halide) intermediate in the non-hemeiron halogenases were synthesized and examined for their inherent reactivity with tertiary carbon radicals. Selective hydroxylation occurs for these cis-FeIII(OH)(X) (X = Cl, Br) complexes in a radical rebound-like process. In contrast, a cis-FeIII(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.
Authors: Sunder N Dhuri; Kyung-Bin Cho; Yong-Min Lee; Sun Young Shin; Jin Hwa Kim; Debasish Mandal; Sason Shaik; Wonwoo Nam Journal: J Am Chem Soc Date: 2015-06-29 Impact factor: 15.419
Authors: Jhumpa Mukherjee; Robie L Lucas; Matthew K Zart; Douglas R Powell; Victor W Day; A S Borovik Journal: Inorg Chem Date: 2008-05-23 Impact factor: 5.165