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

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Abstract

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 phosphorus donors is relatively underexplored. Here, we report aluminum dihydride and dimethyl complexes supported by amido-phosphine ligands, and study their coordination behavior in solution and in the solid state. All complexes exist as κ2-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 κ2-N,N complexes. Thus, importantly for catalytic activity, we find that the coordination behavior of the phosphorus 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 catalytic activity.
Original languageEnglish
JournalInorganic Chemistry
Early online date14 Aug 2019
DOIs
Publication statusE-pub ahead of print - 14 Aug 2019

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