Three Generations of Cobalt Porphyrins as Catalysts in the Oxidation of Cycloalkanes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F19%3A00512003" target="_blank" >RIV/61388955:_____/19:00512003 - isvavai.cz</a>

Výsledek na webu

<a href="http://hdl.handle.net/11104/0302226" target="_blank" >http://hdl.handle.net/11104/0302226</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cssc.201802198" target="_blank" >10.1002/cssc.201802198</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Three Generations of Cobalt Porphyrins as Catalysts in the Oxidation of Cycloalkanes

Popis výsledku v původním jazyce

Three generations of cobalt porphyrins were synthesized, physicochemically characterized by FTIR and UV/Vis spectroscopy as well as cyclic voltammetry and applied as catalysts in the oxidation of cycloalkanes with atmospheric molecular oxygen under mild conditions. All examined catalysts were active in the tested reaction, and their catalytic activity varied with the nature and number of substituents on the porphyrin ring. Introduction of electron-withdrawing or electron-donating substituents at the porphyrin rings increases the activity of metalloporphyrin complexes. It was found, for the first time, that generation II cobalt porphyrins show higher activity in cycloalkane oxidation than cobalt porphyrins of generation III. The lower catalytic activity of generation III cobalt porphyrins can be attributed to the saddle-shaped deformation of the porphyrin macrocycle. DFT modeling of Co porphyrins and their interactions with molecular oxygen provided explanations for the observed effects. On the basis of prior reports and the obtained results, a reaction mechanism is proposed and discussed.

Název v anglickém jazyce

Three Generations of Cobalt Porphyrins as Catalysts in the Oxidation of Cycloalkanes

Popis výsledku anglicky

Three generations of cobalt porphyrins were synthesized, physicochemically characterized by FTIR and UV/Vis spectroscopy as well as cyclic voltammetry and applied as catalysts in the oxidation of cycloalkanes with atmospheric molecular oxygen under mild conditions. All examined catalysts were active in the tested reaction, and their catalytic activity varied with the nature and number of substituents on the porphyrin ring. Introduction of electron-withdrawing or electron-donating substituents at the porphyrin rings increases the activity of metalloporphyrin complexes. It was found, for the first time, that generation II cobalt porphyrins show higher activity in cycloalkane oxidation than cobalt porphyrins of generation III. The lower catalytic activity of generation III cobalt porphyrins can be attributed to the saddle-shaped deformation of the porphyrin macrocycle. DFT modeling of Co porphyrins and their interactions with molecular oxygen provided explanations for the observed effects. On the basis of prior reports and the obtained results, a reaction mechanism is proposed and discussed.

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

2019

Kód důvěrnosti údajů

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

Název periodika

ChemSusChem

ISSN

1864-5631

e-ISSN

—

Svazek periodika

12

Číslo periodika v rámci svazku

3

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

8

Strana od-do

684-691

Kód UT WoS článku

000459739200013

EID výsledku v databázi Scopus

2-s2.0-85057978093