Carbon dioxide reduction by an Al–O–P frustrated Lewis pair

Wickemeyer, Lucas; Aders, Niklas; Mix, Andreas; Neumann, Beate; Stammler, Hans‐Georg; Cabrera-Trujillo, Jorge Juan; Fernández, Israel; Mitzel, Norbert W.

doi:10.1039/d2sc01870e

Cited by 20 publications

(25 citation statements)

References 65 publications

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“…When combining 1 and 2 with the sterically more demanding tert ‐butylnitrile (pivalonitrile), only 1 reacted with the substrate (Scheme 5). For this product, the 1 H NMR signals for the t Bu group attached to the phosphorus atom are slightly downfield‐shifted to 1.26 ppm compared to free 1 (1.20 ppm) [26] . This goes along with an atypical marginal shift of the 31 P{ 1 H} signal to 134.2 ppm from 142.6 ppm.…”

Section: Resultsmentioning

confidence: 87%

“…[30] As reported previously, the reaction of 1 with CO 2 gives the corresponding adduct as an isolable solid. [26] When reacting compound 2 with CO 2 at ambient temperature in a closed NMR tube, two distinct sets of signals are observed: one is that of the free FLP 2, the other belongs to the signals of the CO 2 adduct, the simultaneous presence of both indicates reversible binding of CO 2 (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

“…CO 2 (99.5 %, Linde), benzil (98 %, Alfa Aesar), but‐3‐en‐2‐one (99 %, Sigma Aldrich) and phenylacetylene (98 %, fluorochem) were used without further purification. Di‐ tert ‐butylphosphine oxide and t Bu 2 P−O−AlBis 2 ( 1 ) were prepared according to a literature procedure [26] . NMR spectra were recorded using Bruker Avance III 600, Avance III 500, Avance III 500 HD and Avance III 300 spectrometer at ambient temperature if not stated otherwise.…”

Section: Methodsmentioning

confidence: 99%

“…This FLP readily forms an adduct with CO 2 and reversibly activates molecular hydrogen at ambient temperature and pressure. Furthermore, the H 2 ‐addition product was used to stoichiometrically reduce CO 2 which resulted in the formation of a formic acid adduct [26] …”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, the H 2 -addition product was used to stoichiometrically reduce CO 2 which resulted in the formation of a formic acid adduct. [26] Intending to expand the scope of geminal oxygen-bridged FLP, we report here the preparation of the FLP tBu 2 PÀ OÀ Si-(C 2 F 5 ) 3 (2) and its reactivity regarding adduct formation reactions compared to that of 1.…”

Section: Introductionmentioning

confidence: 99%

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Differences in the Reactivity of Geminal Si−O−P and Al−O−P Frustrated Lewis Pairs

Wickemeyer

Hartmann

Neumann

et al. 2022

Chemistry A European J

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The new oxygen‐bridged geminal Si/P Frustrated Lewis Pair (FLP) tBu2P−O−Si(C2F5)3 (2) is able to reversibly bind carbon dioxide at ambient temperature. We compared its reactivity towards benzil, but‐3‐en‐2‐one, nitriles and phenylacetylene to that of the Al/P FLP tBu2P−O−AlBis2 (Bis=−CH(SiMe3)2) (1). When reacted with benzil, both, 1 and 2, form the 1,2‐addition product, but in the Si/P FLP 2, the second carbonyl function additionally binds to the silicon atom. With but‐3‐en‐2‐one 2 forms the 1,2‐addition product, while 1 binds in 1,4‐position. The reaction with acetonitrile yielded an unexpected etheneimine adduct for both systems, while only 1 reacted with tert‐butylnitrile. With benzonitrile and acrylonitrile, 2 showed reversible addition to the C≡N bond and 1 forms a stable adduct with benzonitrile. Solely 1 shows reactivity towards phenylacetylene affording a mixture of the CH deprotonation adduct tBu2P(H)−O−AlBis2(CCPh) and the FLP −C≡C 1,2‐addition adduct under ring formation. All compounds were characterized by multinuclear NMR spectroscopy, XRD and elemental analysis.

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Section: Resultsmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Differences in the Reactivity of Geminal Si−O−P and Al−O−P Frustrated Lewis Pairs

Wickemeyer

Hartmann

Neumann

et al. 2022

Chemistry A European J

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Selektive 3,3‐Umlagerung von Azobenzolen nach Komplexierung durch ein frustriertes Lewis–Paar

Wickemeyer

Fernández²,

Neumann

et al. 2023

Angewandte Chemie

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Die Reaktion der sauerstoffverbrückten frustrierten Lewis-Paare (FLPs) tBu 2 PÀ OÀ Si(C 2 F 5 ) 3 (1) und tBu 2 PÀ OÀ AlBis 2 (2) mit Azobenzol unter UV-Bestrahlung ergab eine selektive Komplexierung des cis-Isomers. Das Additionsprodukt von 2 ist stabil, während das Addukt von 1 in Lösung ähnlich einer [3,3]-ortho-Benzidin-Umlagerung durch Spaltung der NÀ N-Bindung, Sättigung der Stickstoffatome mit Wasserstoffatomen und Bildung einer neuen Bindung zwischen zwei ortho-Phenylkohlenstoffatomen isomerisiert. Ähnliche Umlagerungen finden mit verschiedenen parasubstituierten Azobenzolen (R = Me, OMe, Cl) und Di(2-naphthyl)diazen statt, während ortho-methylierte Azoverbindungen keine Addukte mit 1 bilden. Alle Addukte wurden mit multinuklearer NMR-Spektroskopie und Elementaranalysen charakterisiert und der Mechanismus der Umlagerung mittels quantenchemischer Berechnungen untersucht.

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Aluminium in der Chemie der Frustrierten Lewis‐Paare

Krämer

2024

Angewandte Chemie

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This review article describes the development of the use of aluminum compounds in the chemistry of frustrated Lewis pairs (FLPs) over the last 14 years. It also discusses the synthesis, reactivity and catalytic applications of intermolecular, intramolecular and so‐called hidden FLPs with phosphorus, nitrogen and carbon Lewis bases. The intrinsically higher acidity of aluminum compounds compared to their boron analogs opens up different reaction pathways. The results are presented in a more or less chronological order. It is shown that Al FLPs react with a variety of polar and non‐polar substrates and form both stable adducts and reversibly activate bonds. Consequently, some catalytic applications of the title compounds were presented such as dimerization of alkynes, hydrogenation of tert‑butyl ethylene and imines, C–F bond activation, reduction of CO2, dehydrogenation of amine borane and transfer of ammonia. In addition, various Al FLPs were used as initiators in polymerization reactions.

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Carbon dioxide reduction by an Al–O–P frustrated Lewis pair

Abstract: The reaction of tBu2P(O)H with Bis2AlH (Bis=CH(SiMe3)2) afforded the adduct tBu2P(H)–O–Al(H)Bis2 (3). It slowly releases H2 to form the first oxygen-bridged geminal Al/P Frustrated Lewis Pair tBu2P–O–AlBis2. It is capable...

Cited by 20 publications

References 65 publications

Differences in the Reactivity of Geminal Si−O−P and Al−O−P Frustrated Lewis Pairs

Differences in the Reactivity of Geminal Si−O−P and Al−O−P Frustrated Lewis Pairs

Selektive 3,3‐Umlagerung von Azobenzolen nach Komplexierung durch ein frustriertes Lewis–Paar

Aluminium in der Chemie der Frustrierten Lewis‐Paare

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