Experimentelle Bestimmung des aktiven Zentrums im heteronuklearen Redox‐System [AlVOx]+./CO/N2O (x=3, 4) durch Gasphasen‐Infrarotspektroskopie

Debnath, Sreekanta; Knorke, Harald; Schöllkopf, Wieland; Zhou, Shaodong; Asmis, Knut R.; Schwarz, Helmut

doi:10.1002/ange.201804056

Angewandte Chemie

2018

DOI: 10.1002/ange.201804056

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Experimentelle Bestimmung des aktiven Zentrums im heteronuklearen Redox‐System [AlVO_x]^+./CO/N₂O (x=3, 4) durch Gasphasen‐Infrarotspektroskopie

Sreekanta Debnath

Harald Knorke

Wieland Schöllkopf

et al.

Abstract: Das aktive Zentrum der Sauerstoffatom-Übertragungsreaktion [AlVO 4 ] + C + CO![AlVO 3 ] + C + CO 2 wurde durch schwingungsspektroskopische Untersuchungen an kryogenen Ionen in Kombination mit Elektronenstrukturberechnungen bestimmt. Infrarot-Photodissoziationsspektren der entsprechenden He-und CO-Komplexed ieser heteronuklearen Metalloxidkationen zeigen, dass [AlVO 3 ] + C im Unterschied zu [AlVO 4 ] + C keine endständige Al-O t -Gruppe mehr enthält, sehr wohl aber noch die V = O t -Gruppe aufweist. Somit ents… Show more

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Cited by 10 publications

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Helium Tagging of Protonated Methane in Messenger Spectroscopy: Does It Interfere with the Fluxionality of CH₅⁺?

Uhl

Marx

2018

Angewandte Chemie

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Messenger infrared predissociation spectroscopy is an powerful technique to investigate elusive molecules. Despite accumulating evidence that 4He‐tagging has a minor effect on structure due to its weak interactions, its impact on intramolecular large‐amplitude motion is much less clear. Using one of the most floppy molecules known, protonated methane, we investigate to what extent helium tags perturb its salient fluxionality, underlying full hydrogen scrambling. Bosonic path integral quantum simulations show that the impact of attaching up to four 4He messengers to CH5+ is negligible compared to the non‐tagged bare species. This non‐invasive nature is unrelated to the bosonic character of 4He. Yet, hydrogen scrambling has a pronounced effect on the microsolvation shell pattern of CH5+⋅Hen that emerges as a result of tagging. These findings should provide impetus to explore the power of He‐tagging, particularly in the realm of weakly bound intermolecular complexes.

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Helium Tagging of Protonated Methane in Messenger Spectroscopy: Does It Interfere with the Fluxionality of CH₅⁺?

Uhl

Marx

2018

Angewandte Chemie

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Über die besondere Rolle des Stickstoffliganden in den durch [NbN]⁺ katalysierten Redoxreaktionen von N₂O/CO in der Gasphase

et al. 2019

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Die durch das Übergangsmetallnitrid-Ion [NbN] + vermittelte,katalytischeR eduktion von N 2 Odurch CO wurde unter thermischen Bedingungen in der Gasphase mittels FT-ICR-Massenspektrometrie und quantenchemischenR echnungen untersucht. Während das [NbN] + /[ONbN] + -System die Oxidation von CO durch N 2 Ok atalysiert, ermçglichen die Systeme [Nb] + /[NbO] + und [NbO] + /[Nb(O) 2 ] + zwar die Oxidation von [Nb] + und [NbO] + durch N 2 O, jedochr eagieren weder [NbO] + noch [Nb(O) 2 ] + bei Zimmertemperatur mit CO.D ie Ursachen dieser durch den Stickstoffliganden hervorgerufenen, deutlichunterschiedlichen Reaktivitäten wurden mit quantenchemischenR echnungen ermittelt.

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Direct Identification of Acetaldehyde Formation and Characterization of the Active Site in the [VPO₄]^.+/C₂H₄ Couple by Gas‐Phase Vibrational Spectroscopy

Debnath

Schlangen

et al. 2019

Angewandte Chemie

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The gas‐phase reaction of the heteronuclear oxide cluster [VPO4].+ with C2H4 is studied under multiple collision conditions at 150 K using cryogenic ion‐trap vibrational spectroscopy combined with electronic structure calculations. The exclusive formation of acetaldehyde is directly identified spectroscopically and discussed in the context of the underlying reaction mechanism. In line with computational predictions it is the terminal P=O and not the V=O unit that provides the oxygen atom in the barrier‐free thermal C2H4→CH3CHO conversion. Interestingly, in the course of the reaction, the emerging CH3CHO product undergoes a rather complex intramolecular migration, coordinating eventually to the vanadium center prior to its liberation. Moreover, the spectroscopic structural characterization of neutral C2H4O deserves special mentioning as in most, if not all, ion/molecule reactions, the neutral product is usually only indirectly identified.

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Experimentelle Bestimmung des aktiven Zentrums im heteronuklearen Redox‐System [AlVO_x]^+./CO/N₂O (x=3, 4) durch Gasphasen‐Infrarotspektroskopie

Cited by 10 publications

References 55 publications

Helium Tagging of Protonated Methane in Messenger Spectroscopy: Does It Interfere with the Fluxionality of CH₅⁺?

Helium Tagging of Protonated Methane in Messenger Spectroscopy: Does It Interfere with the Fluxionality of CH₅⁺?

Über die besondere Rolle des Stickstoffliganden in den durch [NbN]⁺ katalysierten Redoxreaktionen von N₂O/CO in der Gasphase

Direct Identification of Acetaldehyde Formation and Characterization of the Active Site in the [VPO₄]^.+/C₂H₄ Couple by Gas‐Phase Vibrational Spectroscopy

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Experimentelle Bestimmung des aktiven Zentrums im heteronuklearen Redox‐System [AlVOx]+./CO/N2O (x=3, 4) durch Gasphasen‐Infrarotspektroskopie

Cited by 10 publications

References 55 publications

Helium Tagging of Protonated Methane in Messenger Spectroscopy: Does It Interfere with the Fluxionality of CH5+?

Helium Tagging of Protonated Methane in Messenger Spectroscopy: Does It Interfere with the Fluxionality of CH5+?

Über die besondere Rolle des Stickstoffliganden in den durch [NbN]+ katalysierten Redoxreaktionen von N2O/CO in der Gasphase

Direct Identification of Acetaldehyde Formation and Characterization of the Active Site in the [VPO4].+/C2H4 Couple by Gas‐Phase Vibrational Spectroscopy

Contact Info

Product

Resources

About

Experimentelle Bestimmung des aktiven Zentrums im heteronuklearen Redox‐System [AlVO_x]^+./CO/N₂O (x=3, 4) durch Gasphasen‐Infrarotspektroskopie

Helium Tagging of Protonated Methane in Messenger Spectroscopy: Does It Interfere with the Fluxionality of CH₅⁺?

Helium Tagging of Protonated Methane in Messenger Spectroscopy: Does It Interfere with the Fluxionality of CH₅⁺?

Über die besondere Rolle des Stickstoffliganden in den durch [NbN]⁺ katalysierten Redoxreaktionen von N₂O/CO in der Gasphase

Direct Identification of Acetaldehyde Formation and Characterization of the Active Site in the [VPO₄]^.+/C₂H₄ Couple by Gas‐Phase Vibrational Spectroscopy