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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/LTAUSA17026" target="_blank" >LTAUSA17026: Výzkum struktury a reaktivity hypervalentních Fe(IV)=O komplexů</a><br>

Návaznosti

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

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

—

Svazek periodika

140

Číslo periodika v rámci svazku

43

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

14391-14400

Kód UT WoS článku

000449239700050

EID výsledku v databázi Scopus

2-s2.0-85055336486