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.