Trapping Iron(III)-Oxo Species at the Boundary of the "Oxo Wall": Insights into the Nature of the Fe(III)-O Bond

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10384659" target="_blank" >RIV/00216208:11310/18:10384659 - isvavai.cz</a>

Result on the web

<a href="https://doi.org/10.1021/jacs.8b08950" target="_blank" >https://doi.org/10.1021/jacs.8b08950</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.8b08950" target="_blank" >10.1021/jacs.8b08950</a>

Result language

angličtina

Original language name

Trapping Iron(III)-Oxo Species at the Boundary of the "Oxo Wall": Insights into the Nature of the Fe(III)-O Bond

Original language description

Terminal non-heme iron(IV)-oxo compounds are among the most powerful and best studied oxidants of strong C-H bonds. In contrast to the increasing number of such complexes (&gt;80 thus far), corresponding one-electron-reduced derivatives are much rarer and presumably less stable, and only two iron(III)-oxo complexes have been characterized to date, both of which are stabilized by hydrogen-bonding interactions. Herein we have employed gas-phase techniques to generate and identify a series of terminal iron(III)-oxo complexes, all without built-in hydrogen bonding. Some of these complexes exhibit similar to 70 cm(-1) decrease in nu(Fe-O) frequencies expected for a half-order decrease in bond order upon one-electron reduction to an S = 5/2 center, while others have nu(Fe-O) frequencies essentially unchanged from those of their parent iron(IV)-oxo complexes. The latter result suggests that the added electron does not occupy and orbital with Fe=O antibonding character, requiring an S = 3/2 spin assignment for the nascent Fe-III-O- species. In the latter cases, water is found to hydrogen bond to the Fe-III-O- unit, resulting in a change from quartet to sextet spin state. Reactivity studies also demonstrate the extraordinary basicity of these iron(III)-oxo complexes. Our observations show that metal-oxo species at the boundary of the &quot;Oxo Wall&quot; are accessible, and the data provide a lead to detect iron(III)-oxo intermediates in biological and biomimetic reactions.

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10401 - Organic chemistry

Project

<a href="/en/project/LTAUSA17026" target="_blank" >LTAUSA17026: Investigation of structure and reactivity of hypervalent Fe(IV)=O complex</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2018

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

—

Volume of the periodical

140

Issue of the periodical within the volume

43

Country of publishing house

US - UNITED STATES

Number of pages

10

Pages from-to

14391-14400

UT code for WoS article

000449239700050

EID of the result in the Scopus database

2-s2.0-85055336486