Regioselectivity of substrate hydroxylation versus halogenation by a nonheme iron(IV)-oxo complex: possibility of rearrangement pathways.

Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry
Matthew G Quesne, Sam P de Visser

Abstract

Several nonheme iron enzymes and biomimetic model complexes catalyze a substrate halogenation reaction. Recent computational studies (Borowski et al. J Am Chem Soc 132:12887-12898, 2010) on α-ketoglutarate dependent halogenase proposed an initial isomerization reaction that is important to give halogenated products. We present here a series of density functional theory calculations on a biomimetic model complex-[Fe(IV)(O)(TPA)Cl](+), where TPA is tris(2-pyridylmethyl)amine-and investigate the mechanisms of substrate halogenation versus hydroxylation using the reactant and its isomer where the oxo and chloro groups have changed positions. We show here that the reactions occur on a dominant quintet spin state surface, although the reactants are in a triplet state. Despite the fact that the reactants can exist in two stable isomers with the oxo group either trans or cis to the axial ligand, they react differently with substrates, where one gives dominant hydroxylation and the other gives dominant chlorination of substrates. The ligand in the cis position of the oxo group is found to be active in the reaction mechanism and donated to the substrate during the reaction. A detailed thermochemical analysis of possible reaction mechanis...Continue Reading

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Citations

May 28, 2016·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Tibor András RokobLubomír Rulíšek
Aug 6, 2014·Chemical Communications : Chem Comm·Oriol PlanasMiquel Costas
May 16, 2019·Physical Chemistry Chemical Physics : PCCP·Matthew G QuesneC Richard A Catlow
Apr 30, 2019·Frontiers in Chemistry·Matthew G QuesneC Richard A Catlow
Dec 29, 2020·Journal of the American Chemical Society·Vishal YadavDavid P Goldberg
Sep 8, 2021·Inorganic Chemistry·Justin L LeeA S Borovik

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