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What Factors Tune the Chemical Equilibrium between the Metal-Iodosylarene Oxidants and the High-Valent Metal-Oxo Ones?

Abstract

Metal-iodosylarene complexes (1) and high-valent metal-oxo complexes (2) are two key reactive intermediates in oxygenation reactions. Extensive experimental efforts have been carried out to explore the structure-function relatioship of these two elusive oxidants, however, controversial proposals based on these experimental results and the missing mechanistic detals call for the interplay of the theoretical approach with these existing experimental one, especially for the factors which tune the chemical equilibrium between two oxidants 1 and 2. Herein, density functional calculations had been performed and the results demonstrated that the effect of triflate counterions (OTf) is not the well known axial ligand effect. Instead, it works via a novel halogen bond interaction. Such halogen bond interaction not only increases the reaction rate of reversible reactions, but also makes the equilibrium point shift to the direction of the metal-iodosylarene oxidant, compared with the non-halogen bond case. Experimental observed species with a signal of S = 5/2 was identified as an OTf-halogen-bonding iron(III)-iodosylbenzene species (1d in Fig. 1). The substituent effects of iodoarenes were also studied and the results show that the more fluorine-substitution, the higher reaction barrier and the smaller amount of the metal-iodosylarene oxidant in the oxidation system. Our theoretical study will help the researchers in the biomimetic oxidation field have a more profound knowledge on the metal-iodosylarene chemistry and design more rational catalysts.

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Publication details

The article was received on 29 Sep 2018, accepted on 06 Dec 2018 and first published on 06 Dec 2018


Article type: Paper
DOI: 10.1039/C8CP06117C
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    What Factors Tune the Chemical Equilibrium between the Metal-Iodosylarene Oxidants and the High-Valent Metal-Oxo Ones?

    L. Yang, F. Wang, J. Gao and Y. Wang, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP06117C

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