The Reactivity of Primary and Secondary Amines, Secondary Phosphanes and N-Heterocyclic Carbenes towards Group-13 Metal(I) Halides

摘要

The reactions of a variety of primary and secondary amines and secondary phosphanes with "GaI" have been examined. In all cases disproportionation reactions occurred which led to the gallium(II) iodide complexes [Ga_2I_4(L)_2] [L = NCyH_2, NtBuH_2, NCy_2H, PCy_2H or PtBu_2H (Cy = cyclohexyl)]. All complexes have been crystallographically characterised and have been shown to be dimers possessing Ga-Ga bonds. The reaction of the sterically hindered N-heterocyclic carbene IPr [:CN(Ar)C_2H_2N(Ar) (Ar = C_6H_3iPr-2,6)] with "GaI" was also carried out and the novel salt [Ga_2I_5(IPr)][IPr)][IPrH] was formed in good yield and crystallographically characterised. Finally, the related reaction of the less hindered cyclic carbene IMe [:CN(Me)C_2Me_2n(Me)] with InCl gave a low yield of the crystallographically characterised salt [{InCl(IMe)}_2(μ-Cl)(μ-O)][Cl] which presumably forms due to the presence of adventitious oxygen in the reaction mixture.