Organoaluminium complexes incorporating an amido phosphine chelate with a pendant amine arm

Abstract

The palladium-catalyzed aryl amination of 1-bromo-2-fluorobenzene with N,N-dimethylethylenediamine quantitatively produces N-(dimethylaminoethyl)-2-fluoroaniline, which subsequently reacts with KPPh2 in 1,4-dioxane to afford N-(dimethylaminoethyl)-2-diphenylphosphinoaniline (H[PNN]). The reactions of trialkylaluminium with H[PNN] in toluene generate the corresponding aluminium dialkyl complexes [PNN]AlR2 (R = Me, Et, i-Bu). The solution NMR spectroscopic and X-ray crystallographic studies are indicative of a trigonal bipyramidal geometry for these aluminium complexes in which the amino nitrogen atom is trans to the phosphorus donor of the [PNN]- ligand. This study presents rare examples of structurally characterized, five-coordinate aluminium hydrocarbyl complexes supported by phosphine-derived ligands.