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

The reactivity of the Ga/P-based frustrated Lewis pair (FLP) Mes(2)P-C[=C(H)-Ph]-(GaBu2)-Bu-t (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 H-2 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 fluoride ion affinity (including the B and In analogues). The Al compound is the strongest Lewis acid; the Ga FLP is significantly weaker but is a stronger F-acceptor in comparison to the unknown analogues of B and In. These results reflect the different reactivities of these FLPs and may help to develop FLPs with finely adjusted properties.