MCl₂Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P₂-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

Abstract

Two equivalents of the phosphinylvinyl Grignard reagent Mes2PC­[MgCl­(THF)2]CHPh (2) reacted with MeGaCl2, EtGaCl2, or MeInCl2 by salt elimination and formation of the frustrated Lewis pairs 4–6, which have two Lewis basic P atoms in their molecular backbones. These FLPs coordinated and solubilized MCl2 compounds (M = Zn, Cd, Hg) by the chelating coordination of the Zn, Cd, or Hg atoms with phosphorus. The interaction of one Cl atom with the Lewis acidic Ga or In atoms resulted in the formation of norbornane type molecular structures with M–Cl–E bridges (E = Ga, In) and relatively weak M–Cl bonds. The products showed a fascinating dynamic behavior in solution, which gave rise to highly complex NMR spectra. The reaction of 4 with AuCl resulted in cleavage of the Au–Cl bond and the transfer of the Cl atom to the Lewis acidic Ga atom.