English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

High spin oxoiron(IV) complexes have been proposed to be a key intermediate in numerous nonheme metalloenzymes. The successful detection of similar complexes has been reported for only two synthetic systems. A new synthetic high spin oxoiron(IV) complex is now reported that can be prepared from a well-characterized oxoiron(III) species. This new oxoiron(IV) complex can also be prepared from a hydroxoiron(III) species via a proton-coupled electron transfer process--a first in synthetic chemistry. The oxoiron(IV) complex has been characterized with a variety of spectroscopic methods: FTIR studies showed a feature associated with the Fe-O bond at nu(Fe(16)O) = 798 cm(-1) that shifted to 765 cm(-1) in the (18)O complex; Mossbauer experiments show a signal with an delta = 0.02 mm/s and |DeltaE(Q)| = 0.43 mm/s, electronic parameters consistent with an Fe(IV) center, and optical spectra had visible bands at lambda(max) = 440 (epsilon(M) = 3100), 550 (epsilon(M) = 1900), and 808 (epsilon(M) = 280) nm. In addition, the oxoiron(IV) complex gave the first observable EPR features in the parallel-mode EPR spectrum with g-values at 8.19 and 4.06. A simulation for an S = 2 species with D = 4.0(5) cm(-1), E/D = 0.03, sigma(E/D) = 0.014, and g(z) = 2.04 generates a fit that accurately predicted the intensity, line shape, and position of the observed signals. These results showed that EPR spectroscopy can be a useful method for determining the properties of high spin oxoiron(IV) complexes. The oxoiron(IV) complex was crystallized at -35 degrees C, and its structure was determined by X-ray diffraction methods. The complex has a trigonal bipyramidal coordination geometry with the Fe-O unit positioned within a hydrogen bonding cavity. The Fe(IV)-O unit bond length is 1.680(1) A, which is the longest distance yet reported for a monomeric oxoiron(IV) complex.

journal of the american chemical society

Formation, Structure, and EPR Detection of a High Spin FeIV—Oxo Species Derived from Either an FeIII—Oxo or FeIII—OH Complex