Hydrocarbon Oxidation by an Exposed, Multiply Bonded Iron(III) Oxo Complex

Juan A Valdez-Moreira; Daniel M Beagan; Hao Yang; Joshua Telser; Brian M Hoffman; Maren Pink; Veronica Carta; Jeremy M Smith

doi:10.1021/acscentsci.1c00890

Hydrocarbon Oxidation by an Exposed, Multiply Bonded Iron(III) Oxo Complex

ACS Cent Sci. 2021 Oct 27;7(10):1751-1755. doi: 10.1021/acscentsci.1c00890. Epub 2021 Sep 23.

Authors

Juan A Valdez-Moreira¹, Daniel M Beagan¹, Hao Yang², Joshua Telser³, Brian M Hoffman², Maren Pink¹, Veronica Carta¹, Jeremy M Smith¹

Affiliations

¹ Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington Indiana 47405, United States.
² Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
³ Department of Biological, Physical and Health Sciences, Roosevelt University, Chicago, Illinois 60605, United States.

Abstract

The iron oxo unit, [Fe=O] ⁿ⁺ is a critical intermediate in biological oxidation reactions. While its higher oxidation states are well studied, relatively little is known about the least-oxidized form [Fe^III=O]⁺. Here, the thermally stable complex PhB(AdIm)₃Fe=O has been structurally, spectroscopically, and computationally characterized as a bona fide iron(III) oxo. An unusually short Fe-O bond length is consistent with iron-oxygen multiple bond character and is supported by electronic structure calculations. The complex is thermally stable yet is able to perform hydrocarbon oxidations, facilitating both C-O bond formation and dehydrogenation reactions.