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

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 2 I 4 (L) 2 ] [L = NCyH 2 , N t BuH 2 , NCy 2 H, PCy 2 H or P t Bu 2 H (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 2 H 2 N(Ar) (Ar = C 6 H 3 i Pr 2 ‐2,6)] with “GaI” was also carried out and the novel salt [Ga 2 I 5 (IPr)][IPrH] was formed in good yield and crystallographically characterised. Finally, the related reaction of the less hindered cyclic carbene IMe [ : CN(Me)C 2 Me 2 N(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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)