Influence of the Lewis Acidity of Gallium Atoms on the Reactivity of a Frustrated Lewis Pair: Experimental and Theoretical Studies

Abstract

The reactivity of the Ga/P-based frustrated Lewis pair (FLP) Mes2P–C[═C(H)–Ph]–GatBu2 (3) is influenced by the relatively weak Lewis acidity of its Ga atom and differs significantly from that of the analogous Al compound 1. The adduct of 3 with CO2 was only detectable at low temperature by NMR spectroscopy. Benzaldehyde was coordinated only via a Ga–O bond; the P atom was not involved. In contrast, a relatively persistent adduct was formed with soft CS2 to yield a five-membered GaCPCS heterocycle. Dehydrocoupling with H3B←NHMe2 afforded the dimeric amidoborane (H2B–NMe2)2, while an adduct with a GaCPBN heterocycle was isolated with the sterically less shielded ammonia–borane H3B←NH3. The latter product was unstable in solution and decomposed by H2 elimination and formation of oligomeric BN compounds. Small quantities of 3 catalyzed hydrogen transfer from H3B←NH3 to an imine. The Lewis acidities of the Al/P- and Ga/P-based FLPs were examined by experiments (Gutmann–Beckett method) and by calculation of the...