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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 of reversibly binding molecular hydrogen to afford 3, shown by NMR and H/D scrambling experiments, and forms a 1,2-adduct with CO₂. Importantly, the H₂ adduct 3 reduces CO₂ in a stoichiometric reaction leading to the formic acid adduct tBu₂P(H)-O-Al(CO₂H)Bis₂. The formation of the different species was explored by density functional theory calculations which provide support for the experimental results. All products were characterized by NMR spectroscopy as well as X-ray diffraction experiments and elemental analyses.

SUBMITTER: Wickemeyer L

PROVIDER: S-EPMC9278507 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Carbon dioxide reduction by an Al-O-P frustrated Lewis pair.

Wickemeyer Lucas L Aders Niklas N Mix Andreas A Neumann Beate B Stammler Hans-Georg HG Cabrera-Trujillo Jorge J JJ Fernández Israel I Mitzel Norbert W NW

Chemical science 20220602 27

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 of reversibly binding molecular hydrogen to afford 3, shown by NMR and H/D scrambling experiments, and forms a 1,2-adduct with CO2. Importantly, ...[more]

PMID: 35919415

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