ABSTRACT
An Al/P-based frustrated Lewis pair (FLP) reacted with PhMgCl by an unexpected transmetalation and formation of a phosphinylvinyl Grignard reagent. This compound is well suited for the transfer of the basic FLP component to other Lewis acidic metal atoms and allowed the generation of a Ga/P and an In/P2 FLP. The Ga FLP showed a behavior different to that of the corresponding Al FLP, the In FLP allowed the chelating coordination of an Au atom by Au-Cl bond activation.
ABSTRACT
The Al/P-based frustrated Lewis pair (FLP) Mes2P-C(âCH-Ph)-Al(CMe3)2 (1) reacted with boron halides BX3 (X = F, Cl, Br, I) as an ambiphilic ligand to form complexes (2-5) in which the boron atoms were coordinated to phosphorus and one of the halogen atoms to aluminum. Nonplanar five-membered heterocycles resulted that had five different ring atoms (AlCPBX). The distance of the bridging halogen atoms to the AlCPB plane increased steadily with the radius of the halogen atoms. Only the BF3 adduct showed a dynamic behavior in solution at room temperature with equivalent tert-butyl or mesityl groups in the NMR spectra, while in other cases, the rigid conformation led to the magnetic inequivalence of the substituents at Al and P with well-resolved signals for each group. The BBr3 and BI3 complexes underwent in solution at room temperature a spontaneous stereoselective rearrangement with the concomitant release of isobutene. The obtained products, Mes2P-(µ-CâCH-Ph)(µ-HBX2)-AlX(CMe3) (6 and 7) may be viewed as unique adducts of a modified new Al/P-based FLP, Mes2P-C(âCH-Ph)-AlX(CMe3) (X = Br, I), with dihalogenboranes, HBX2. The trapped boranes are either completely unknown (X = I) or unstable in the free form. Quantum-chemical calculations suggest an ionic rearrangement mechanism via the formation of a borenium cation, ß-hydride elimination, and hydride transfer. The bromine migration from boron to aluminum corresponds to a formal suprafacial 1,3-sigmatropic rearrangement.
