A Synthetically Generated LFe IVOH n Complex

Weitz, Andrew C.; Mills, Matthew R.; Ryabov, Alexander D.; Collins, Terrence J.; Guo, Yisong; Bominaar, Emile L.; Hendrich, Michael P.

doi:10.1021/acs.inorgchem.8b03200

Title: A Synthetically Generated LFe ^IVOH _n Complex

Journal Article · 22 January 2019 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.8b03200 · OSTI ID:1495452

Weitz, Andrew C. ^[1];

^[1];

^[1]

Carnegie Mellon Univ., Pittsburgh, PA (United States)

High-valent Fe–OH species are important intermediates in hydroxylation chemistry. Such complexes have been implicated in mechanisms of oxygen-activating enzymes and have thus far been observed in Compound II of sulfur-ligated heme enzymes like cytochrome P450. Attempts to synthetically model such species have thus far seen relatively little success. We report the first synthetic Fe^IVOH_n complex has been generated and spectroscopically characterized as either [LFe^IVOH]^– or [LFe^IVOH₂]⁰, where H₄L = Me₄C₂(NHCOCMe₂NHCO)₂CMe₂ is a variant of a tetra-amido macrocyclic ligand (TAML). The steric bulk provided by the replacement of the aryl group with the –CMe₂CMe₂– unit in this TAML variant prevents dimerization in all oxidation states over a wide pH range, thus allowing the generation of Fe^IVOH_n in near quantitative yield from oxidation of the [LFe^IIIOH₂]^– precursor.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: Heinz Endowments; National Institutes of Health (NIH); National Science Foundation (NSF); USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1495452

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 3 Vol. 58; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Title: A Synthetically Generated LFe IVOH n Complex

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Title: A Synthetically Generated LFe ^IVOH _n Complex