Flexible Coordination of N,P-Donor Ligands in Aluminum Dimethyl and Dihydride Complexes

[Image: see text] Aluminum hydrides, once a simple class of stoichiometric reductants, are now emerging as powerful catalysts for organic transformations such as the hydroboration or hydrogenation of unsaturated bonds. The coordination chemistry of aluminum hydrides supported by P donors is relatively underexplored. Here, we report aluminum dihydride and dimethyl complexes supported by amidophosphine ligands and study their coordination behavior in solution and in the solid state. All complexes exist as κ(2)-N,P complexes in the solid state. However, we find that for amidophosphine ligands bearing bulky aminophosphine donors, aluminum dihydride and dimethyl complexes undergo a “ligand-slip” rearrangement in solution to generate κ(2)-N,N complexes. Thus, importantly for catalytic activity, we find that the coordination behavior of the P donor can be modulated by controlling its steric bulk. We show that the reported aluminum hydrides catalyze the hydroboration of alkynes by HBPin and that the variable coordination mode exhibited by the amidophosphine ligand modulates the catalytic activity.