dc.contributor.author
Mebs, Stefan
dc.contributor.author
Beckmann, Jens
dc.date.accessioned
2023-05-22T08:45:24Z
dc.date.available
2023-05-22T08:45:24Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/39377
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-39094
dc.description.abstract
CO2, NO2, and SO2 can be activated in silico with tailor-made light atom tripodal ligand systems carrying particular numbers of Lewis acidic and basic sites in specific relative orientations. In the calculated EO2-adducts (E=C, N, S), considerable E−O bond elongations of 0.1–0.3 Å, decreasing the E=O double bond character, and O−E−O angle alterations, approaching tetrahedral geometry, activate the donor acceptor complexes towards reduction with BH4−. The lone pairs of the P atoms thereby serve as donors towards the central element, C, N, or S, whereas the electron deficient B atoms serve as acceptors. The charge redistribution within the EO2 complex was monitored by a variety of DFT-derived real-space bonding indicators (RSBIs) including bond topologies, non-covalent contact patches, and electron pair basins. For one CO2-complex, the reduction towards methanol and water was conducted via stepwise addition of H− and H+. The most critical steps are the initial CO2 uptake due to potential quenching of the ligand systems in their active state, increasing the kinetic barrier, and the release of methanol and water from the ligand system due to potential ligand poisoning. Unbeneficial side reactions in the stepwise reduction and protonation have to be considered.
en
dc.format.extent
11 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by-nc/4.0/
dc.subject
CO2 reduction
en
dc.subject
Peri-Systems
en
dc.subject
Frustrated Lewis Pairs
en
dc.subject
Density Functional Theory
en
dc.subject
Real-Space Bonding Indicators
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften
dc.title
In Silico Activation of CO2, NO2, and SO2 with Light Atom Molecules and Stepwise Conversion of CO2 into Methanol and Water
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.articlenumber
e202301173
dcterms.bibliographicCitation.doi
10.1002/slct.202301173
dcterms.bibliographicCitation.journaltitle
ChemistrySelect
dcterms.bibliographicCitation.number
17
dcterms.bibliographicCitation.volume
8
dcterms.bibliographicCitation.url
https://doi.org/10.1002/slct.202301173
refubium.affiliation
Physik
refubium.affiliation.other
Institut für Experimentalphysik
refubium.funding
DEAL Wiley
refubium.note.author
Die Publikation wurde aus Open Access Publikationsgeldern der Freien Universität Berlin gefördert.
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.eissn
2365-6549