Reactivity of bulky aminophosphanes towards small molecules: Activation of dihydrogen and carbon dioxide by aminophosphane/borane frustrated Lewis pairs

A series of monoand bisaminophosphanes with formulas R2NPR'R"and (R2N)(2)PR' (R = iPr, Cy; R' = Ph, Cy; R"= iPr) were characterized by X-ray analysis, NMR spectroscopy and computational methods. The common structural futures of these species are short and polarized P-N bonds, a pyramidal geometry at the P atom and an almost planar geometry at the N atoms. According to DFT calculations, these compounds are highly nucleophilic, with nucleophilic centers located on the N and P atoms. Except for species containing a PPh2 moiety, the obtained aminophosphanes are air-stable and do not react with water. They form stable frustrated Lewis pairs with BPh3 or B(C6F5)(3). Monoand bisaminophosphanes in the presence of B(C6F5)(3) activate dihydrogen and carbon dioxide at room temperature. (C) 2020 Elsevier Ltd. All rights reserved.