Theoretical structural and electronic analyses with emphasis on the reactivity of iron oxide prototypes in methane C-H bond activation

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F62690094%3A18450%2F17%3A50005702" target="_blank" >RIV/62690094:18450/17:50005702 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1007/s11144-016-1103-9" target="_blank" >http://dx.doi.org/10.1007/s11144-016-1103-9</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1007/s11144-016-1103-9" target="_blank" >10.1007/s11144-016-1103-9</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Theoretical structural and electronic analyses with emphasis on the reactivity of iron oxide prototypes in methane C-H bond activation

Popis výsledku v původním jazyce

In the present work, a detailed theoretical investigation using B3LYP, CCSD(T) and ZORA-B3LYP calculations has been performed in order to investigate activation processes of methane C-H bond by iron oxide prototype series: FeOmn+ (m = 1, 2; n = 0, 1, 2). The main results indicate that, in accordance with previous experimental findings, only FeO+ monoxide is kinetically and thermodynamically feasible through the hydrogen abstraction mechanism, with an already known pathway described as &quot;oxidative hydrogen migration&quot;. The overall results indicate better thermodynamic and kinetic conditions for all iron monoxides, in relation to iron dioxides. Based on the energy values and the structural parameters, the 4-center abstraction mechanism should be thermodynamically more favorable in relation to the direct abstraction mechanism, due to the lack of Fe-C interaction for the direct abstraction mechanism. The AIM calculations indicate a larger ionic character for the Fe-O+ chemical bond, whereas a mixed participation, relative to ionic and covalent character, was found in chemical bonds of the remaining iron oxides.

Název v anglickém jazyce

Theoretical structural and electronic analyses with emphasis on the reactivity of iron oxide prototypes in methane C-H bond activation

Popis výsledku anglicky

In the present work, a detailed theoretical investigation using B3LYP, CCSD(T) and ZORA-B3LYP calculations has been performed in order to investigate activation processes of methane C-H bond by iron oxide prototype series: FeOmn+ (m = 1, 2; n = 0, 1, 2). The main results indicate that, in accordance with previous experimental findings, only FeO+ monoxide is kinetically and thermodynamically feasible through the hydrogen abstraction mechanism, with an already known pathway described as &quot;oxidative hydrogen migration&quot;. The overall results indicate better thermodynamic and kinetic conditions for all iron monoxides, in relation to iron dioxides. Based on the energy values and the structural parameters, the 4-center abstraction mechanism should be thermodynamically more favorable in relation to the direct abstraction mechanism, due to the lack of Fe-C interaction for the direct abstraction mechanism. The AIM calculations indicate a larger ionic character for the Fe-O+ chemical bond, whereas a mixed participation, relative to ionic and covalent character, was found in chemical bonds of the remaining iron oxides.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2017

Kód důvěrnosti údajů

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

Název periodika

REACTION KINETICS MECHANISMS AND CATALYSIS

ISSN

1878-5190

e-ISSN

—

Svazek periodika

120

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

14

Strana od-do

195-208

Kód UT WoS článku

000396938800014

EID výsledku v databázi Scopus

2-s2.0-84994158674