Upside Down! Crystallographic and Spectroscopic Characterization of an [Fe IV(O syn)(TMC)]2+ Complex

Jai Prakash; Gregory T Rohde; Katlyn K Meier; Eckard Münck; Lawrence Que Jr

doi:10.1021/acs.inorgchem.5b02011

Upside Down! Crystallographic and Spectroscopic Characterization of an [Fe IV(O syn)(TMC)]2+ Complex

Inorg Chem. 2015 Dec 7;54(23):11055-7. doi: 10.1021/acs.inorgchem.5b02011. Epub 2015 Nov 24.

Authors

Jai Prakash¹, Gregory T Rohde¹, Katlyn K Meier², Eckard Münck², Lawrence Que Jr¹

Affiliations

¹ Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota , Minneapolis, Minnesota 55455, United States.
² Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.

PMID: 26615667
DOI: 10.1021/acs.inorgchem.5b02011

Abstract

Fe(II)(TMC)(OTf)2 reacts with 2-(t)BuSO2-C6H4IO to afford an oxoiron(IV) product, 2, distinct from the previously reported [Fe(IV)(Oanti)(TMC)(NCMe)](2+). In MeCN, 2 has a blue-shifted near-IR band, a higher ν(Fe═O), a larger Mössbauer quadrupole splitting, and quite a distinct (1)H NMR spectrum. Structural analysis of crystals grown from CH2Cl2 reveals a complex with the formulation of [Fe(IV)(Osyn)(TMC)(OTf)](OTf) and the shortest Fe(IV)═O bond [1.625(4) Å] found to date.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.