Reactivity of GaX3 with silylamines and thermal decomposition of the compounds [Cl2Ga{NH(SiMe3)}]2 and [Cl3Ga{NH(SiMe3)2}]

The Lewis acid/base adducts [X3Ga{NH(R)(Rʹ)}](X = Cl, R = Rʹ= SiMe3(1), SiMe2Ph (2) and R = But, Rʹ= SiMe3(3); X = Br, R = Rʹ= SiMe3(4) or SiMe2Ph (5)) were synthesised by the 1 : 1 reaction of GaX3 with NH(R)(Rʹ) in hexane solution at room temperature. Dimeric complexes, of the type [X2Ga{NH(R)}]2(X = Cl, R = SiMe3(6), R = SiMe2Ph (7) and R = But(8); X = Br, R = SiMe3(9)) were prepared by the 1 : 1 reaction of GaX3 with NH(R)(R) in CH2Cl2 solution. Compounds 1 and 8 have been structurally characterised. Polycrystalline GaN was obtained from the pyrolysis of compounds 1 and 6 under inert conditions (N2, vacuum) above 500 °C, as shown by the X-ray powder diffraction patterns.