10.1021/ic5009126.s007 Werner Uhl Werner Uhl Christian Appelt Christian Appelt Agnes Wollschläger Agnes Wollschläger Alexander Hepp Alexander Hepp Ernst-Ulrich Würthwein Ernst-Ulrich Würthwein An Al/P-Based Frustrated Lewis Pair as an Efficient Ambiphilic Ligand: Coordination of Boron Trihalides, Rearrangement, and Formation of HBX<sub>2</sub> Complexes (X = Br, I) American Chemical Society 2014 hydride Br BF 3 adduct 2P HBX 2 Complexes solution rearrangement Me boron halides BX 3 BI 3 complexes halogen atoms FLP NMR Lewis Al room temperature Efficient Ambiphilic Ligand 2014-09-02 00:00:00 Dataset https://acs.figshare.com/articles/dataset/An_Al_P_Based_Frustrated_Lewis_Pair_as_an_Efficient_Ambiphilic_Ligand_Coordination_of_Boron_Trihalides_Rearrangement_and_Formation_of_HBX_sub_2_sub_Complexes_X_Br_I_/2259307 The Al/P-based frustrated Lewis pair (FLP) Mes<sub>2</sub>PC­(CHPh)Al­(CMe<sub>3</sub>)<sub>2</sub> (<b>1</b>) reacted with boron halides BX<sub>3</sub> (X = F, Cl, Br, I) as an ambiphilic ligand to form complexes (<b>2</b>–<b>5</b>) 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 BF<sub>3</sub> adduct showed a dynamic behavior in solution at room temperature with equivalent <i>tert</i>-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 BBr<sub>3</sub> and BI<sub>3</sub> complexes underwent in solution at room temperature a spontaneous stereoselective rearrangement with the concomitant release of isobutene. The obtained products, Mes<sub>2</sub>P(μ-CCHPh)­(μ-HBX<sub>2</sub>)AlX­(CMe<sub>3</sub>) (<b>6</b> and <b>7</b>) may be viewed as unique adducts of a modified new Al/P-based FLP, Mes<sub>2</sub>P­C­(CHPh)­AlX­(CMe<sub>3</sub>) (X = Br, I), with dihalogenboranes, HBX<sub>2</sub>. 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, β-hydride elimination, and hydride transfer. The bromine migration from boron to aluminum corresponds to a formal suprafacial 1,3-sigmatropic rearrangement.