28550-87-0Relevant academic research and scientific papers
Determining the Inherent Selectivity for Carbon Radical Hydroxylation versus Halogenation with FeIII(OH)(X) Complexes: Relevance to the Rebound Step in Non-heme Iron Halogenases
Yadav, Vishal,Rodriguez, Rodolfo J.,Siegler, Maxime A.,Goldberg, David P.
supporting information, p. 7259 - 7264 (2020/04/22)
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.
Direct observation of oxygen rebound with an iron-hydroxide complex
Zaragoza, Jan Paulo T.,Yosca, Timothy H.,Siegler, Maxime A.,Mo?nne-Loccoz, Pierre,Green, Michael T.,Goldberg, David P.
supporting information, p. 13640 - 13643 (2017/11/06)
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 metalhydroxide 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.
Sterically Hindered Free Radicals, XIX. - Stable 4,4',4''-Trisubstituted Triphenylmethyl Radicals
Duennebacke, Dieter,Neumann, Wilhelm P.,Penenory, Alicia,Stewen, Ulrich
, p. 533 - 536 (2007/10/02)
The title radicals (4-R-C6H4)3C. (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, have been prepared, the latter four for the first time, and the ESR spectra have been recorded. aoH, amH, and as
