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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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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

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OECD FORD branch

10402 - Inorganic and nuclear chemistry

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2024

Confidentiality

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

Name of the periodical

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Volume of the periodical

53

Issue of the periodical within the volume

27

Country of publishing house

GB - UNITED KINGDOM

Number of pages

17

Pages from-to

11514-11530

UT code for WoS article

001253495700001

EID of the result in the Scopus database

2-s2.0-85197884410