Bulky amidinato complexes and amidine adducts of Al, Ga and In halides

Reactions of a series of bulky amidinate salts M[RC(NAr)2] (M = Li, Na or K; R = H, Fiso; Me, Aiso; But, Piso; Ar=2,6-Pr2iC6H3) with group 13 halides are reported. Treatment of the metal(I) halides, ‘GaI’ or InCl, with [Li(Fiso)] led to disproportionation reactions which gave the first gallium(II)-amidinate complex, [{GaI(Fiso)}2] (7), in addition to the metal(III) complexes, [GaI(Fiso)2] (8) and [InCl(Fiso)2] (10). Moreover, the Ga(II) compounds 7 and [{GaI(Piso)}2] (9) were synthesised in metathesis reactions between amidinate salts and [{GaI2(NHCy2)}2] (Cy=cyclohexyl). Treating [AlMe2(Aiso)], [{AlH2(Piso)}2] or [AlMe2(Piso)] with iodine in toluene led to isolation of the Al(III) iodide complexes [AlI2(Aiso)] (12), [AlI3(AisoH)] (13) and [AlI2(Piso)] (14). The adduct [GaCl3(FisoH)] (16) was obtained from the reactions of either [Na(Fiso)] or FisoH with GaCl3, whilst the amidinium salt [TripH2][InBr4] (17), (Trip = [TrC(NPri)2]−, Tr = 9-triptycenyl) was isolated from the reaction of [Li(Trip)] with InBr3. The X-ray crystal structures of 7, 9, 10, 13, 14, 16 and 17 are reported.

Graphical abstractThe reactions of several bulky amidinate salts with group 13 metal(I), (II) and (III) halides have been carried out. These have led to a variety of amidinato-metal(II) or (III) halide complexes (e.g., see picture) which have been structurally characterised.Figure optionsDownload full-size imageDownload as PowerPoint slide