Bis-(triphenylphosphane) Aluminum Hydride: A Simple Way to Provide, Store, and Use Non-Polymerized Alane for Synthesis

Chempluschem. 2021 Aug 10;86(8):1193-1198. doi: 10.1002/cplu.202100287. Online ahead of print.

Abstract

AlH3 (PPh3 )2 was synthesized as a stable solid being the first known 1 : 2 alane arylphosphane adduct. Although only weakly intra-molecularly coordinated, it displays as a molecular crystal significant inertness against atmospheric humidity and oxygen due to strong steric screening of the alane unit. The compound readily dissociates PPh3 in solution allowing for its use as a Lewis acidic reducing agent. These features lead to an easy to store, easy to use reducing agent that may enable the quantitative investigation of aluminum hydride chemistry including reduction, complexation and hydroalumination reactions. The structure contains two non-equivalent penta-coordinated aluminum centers that despite long Al-P distances of ca. 2.7 Å display unusually high quadrupolar coupling constants CQ of 25.1 and 26.5 in 27 Al solid state NMR measurements. The product was also tested as a reducing agent on a small set of selected compounds with various functional groups.

Keywords: alane adducts; hydrogenation reactions; hydrolysis kinetics; metal hydrides; phospane adducts.