Chemical fixation of atmospheric CO2 in tricopper(II)-carbonato complexes with tetradentate N-donor ligands: reactive intermediates, probable mechanisms, and catalytic and magneto-structural studies

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F24%3A73627694" target="_blank" >RIV/61989592:15310/24:73627694 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt00503a" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt00503a</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4dt00503a" target="_blank" >10.1039/d4dt00503a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Chemical fixation of atmospheric CO2 in tricopper(II)-carbonato complexes with tetradentate N-donor ligands: reactive intermediates, probable mechanisms, and catalytic and magneto-structural studies

Popis výsledku v původním jazyce

In the present era, the fixation of atmospheric CO2 is of significant importance and plays a crucial role in maintaining the balance of carbon and energy flow within ecosystems. Generally, CO2 fixation is carried out by autotrophic organisms; however, the scientific community has paid substantial attention to execute this process in laboratory. In this report, we synthesized two carbonato-bridged trinuclear copper(ii) complexes, [Cu-3(L1)(3)(mu(3)-CO3)](ClO4)(3) (1) and [Cu-3(L2)(3)(mu(3)-CO3)](ClO4)(3) (2) via atmospheric fixation of CO2 starting with Cu(ClO4)(2)center dot 6H(2)O and easily accessible pyridine/pyrazine-based N-4 donor Schiff base ligands L1 and L2, respectively. Under very similar reaction conditions, the ligand framework embedded with the phenolate moiety (HL3) fails to do so because of the reduction of the Lewis acidity of the metal center, inhibiting the formation of a reactive hydroxide bound copper(ii) species, which is required for the fixation of atmospheric CO2. X-ray crystal structures display that carbonate-oxygen atoms bridge three copper(ii) centers in mu(3)syn-anti disposition in 1 and 2, whereas [Cu(HL3)(ClO4)] (3) is a mononuclear complex. Interestingly, we also isolated an important intermediate of atmospheric CO2 fixation and structurally characterized it as an anti-anti mu(2) carbonato-bridged dinuclear copper(ii) complex, [Cu-2(L2)(2)(mu(2)-CO3)](ClO4)(2)center dot MeOH (2-I), providing an in-depth understanding of CO2 fixation in these systems. Variable temperature magnetic susceptibility measurement suggests ferromagnetic interactions between the metal centers in both 1 and 2, and the results have been further supported by DFT calculations. The catalytic efficiency of our synthesized complexes 1-3 was checked by means of catechol oxidase and phenoxazinone synthase-like activities. While complexes 1 and 2 showed oxidase-like activity for aerobic oxidation of o-aminophenol and 3,5-di-tert-butylcatechol, complex 3 was found to be feebly active. ESI mass spectrometry revealed that the oxidation reaction proceeds through the formation of complex-substrate intermediations and was further substantiated by DFT calculations. Moreover, active catalysts 1 and 2 were effectively utilized for the base-free oxidation of benzylic alcohols in the presence of air as a green and sustainable oxidant and catalytic amount of TEMPO in acetonitrile. Various substituted benzylic alcohols smoothly converted to their corresponding aldehydes under very mild conditions and ambient temperature. The present catalytic protocol showcases its environmental sustainability by producing minimal waste.

Název v anglickém jazyce

Chemical fixation of atmospheric CO2 in tricopper(II)-carbonato complexes with tetradentate N-donor ligands: reactive intermediates, probable mechanisms, and catalytic and magneto-structural studies

Popis výsledku anglicky

In the present era, the fixation of atmospheric CO2 is of significant importance and plays a crucial role in maintaining the balance of carbon and energy flow within ecosystems. Generally, CO2 fixation is carried out by autotrophic organisms; however, the scientific community has paid substantial attention to execute this process in laboratory. In this report, we synthesized two carbonato-bridged trinuclear copper(ii) complexes, [Cu-3(L1)(3)(mu(3)-CO3)](ClO4)(3) (1) and [Cu-3(L2)(3)(mu(3)-CO3)](ClO4)(3) (2) via atmospheric fixation of CO2 starting with Cu(ClO4)(2)center dot 6H(2)O and easily accessible pyridine/pyrazine-based N-4 donor Schiff base ligands L1 and L2, respectively. Under very similar reaction conditions, the ligand framework embedded with the phenolate moiety (HL3) fails to do so because of the reduction of the Lewis acidity of the metal center, inhibiting the formation of a reactive hydroxide bound copper(ii) species, which is required for the fixation of atmospheric CO2. X-ray crystal structures display that carbonate-oxygen atoms bridge three copper(ii) centers in mu(3)syn-anti disposition in 1 and 2, whereas [Cu(HL3)(ClO4)] (3) is a mononuclear complex. Interestingly, we also isolated an important intermediate of atmospheric CO2 fixation and structurally characterized it as an anti-anti mu(2) carbonato-bridged dinuclear copper(ii) complex, [Cu-2(L2)(2)(mu(2)-CO3)](ClO4)(2)center dot MeOH (2-I), providing an in-depth understanding of CO2 fixation in these systems. Variable temperature magnetic susceptibility measurement suggests ferromagnetic interactions between the metal centers in both 1 and 2, and the results have been further supported by DFT calculations. The catalytic efficiency of our synthesized complexes 1-3 was checked by means of catechol oxidase and phenoxazinone synthase-like activities. While complexes 1 and 2 showed oxidase-like activity for aerobic oxidation of o-aminophenol and 3,5-di-tert-butylcatechol, complex 3 was found to be feebly active. ESI mass spectrometry revealed that the oxidation reaction proceeds through the formation of complex-substrate intermediations and was further substantiated by DFT calculations. Moreover, active catalysts 1 and 2 were effectively utilized for the base-free oxidation of benzylic alcohols in the presence of air as a green and sustainable oxidant and catalytic amount of TEMPO in acetonitrile. Various substituted benzylic alcohols smoothly converted to their corresponding aldehydes under very mild conditions and ambient temperature. The present catalytic protocol showcases its environmental sustainability by producing minimal waste.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

53

Číslo periodika v rámci svazku

27

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

17

Strana od-do

11514-11530

Kód UT WoS článku

001253495700001

EID výsledku v databázi Scopus

2-s2.0-85197884410