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

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.