Issue 18, 2020

Sluggish reactivity by a nonheme iron(iv)-tosylimido complex as compared to its oxo analogue

Abstract

High-valent iron-nitrido intermediates have been postulated as reactive intermediates in various enzymes, including the nitrogenases and the cytochromes P450, but so far few have been trapped and characterized. As little is known about their oxidative and spectroscopic properties, we decided to create biomimetic models of iron(IV)-imido complexes and compare their structure and reactivity with analogous iron(IV)-oxo systems. In this work we report the synthesis and spectroscopic characterization of a novel [FeIV(NTs)(Bntpen)]2+ complex (Bntpen = N1-benzyl-N1,N2,N2-tris(pyridine-2-ylmethyl)ethane-1,2-diamine) and study its reactivity patterns with respect to hydrogen atom abstraction and nitrogen atom transfer reactions. The work is compared with analogous pentadentate ligand systems as well as with iron(IV)-oxo species with the same ligand features and highlights the differences in chemical properties and reactivity patterns. It is shown that the reactivity is dependent on the metal ligand system that affects the physicochemical properties of the oxidant such as the redox potential, which is the main driving force for the reaction mechanism with substrates.

Graphical abstract: Sluggish reactivity by a nonheme iron(iv)-tosylimido complex as compared to its oxo analogue

Supplementary files

Article information

Article type
Paper
Submitted
03 Jan 2020
Accepted
08 Eph 2020
First published
08 Eph 2020

Dalton Trans., 2020,49, 5921-5931

Sluggish reactivity by a nonheme iron(IV)-tosylimido complex as compared to its oxo analogue

G. Mukherjee, F. G. C. Reinhard, U. K. Bagha, C. V. Sastri and S. P. de Visser, Dalton Trans., 2020, 49, 5921 DOI: 10.1039/D0DT00018C

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