Syntheses of compounds with M-N bonds (M = Li, Ga, In)

The adducts [GaCl3((HNPr2)-Pr-i)] (1) and [InCl3{HN(CH2Ph)(2)}(2)] (2) can be obtained by the reactions of the corresponding metal(III) halides with t he amines. The In amide In(N(c)Hex(2))(3) (3) can be formed by treatment of InCl3 with three equivalents of LiN(c)Hex(2). Reaction with four equivalen ts of LiN(c)Hex(2) leads to the same product. However, the treatment of InC l3 with four equivalents of LiN(CH2Ph)(2) gives the desired metalate [Li(TH F)(4)][In{N(CH2Ph)(2)}(4)] (4). From the corresponding reaction of InCl3 wi th (LiNPr2)-Pr-i no In-containing product could be identified. Instead, the aggregate of LiCl with three units of (LiNPr2)-Pr-i, [Li-4((NPr2)-Pr-i)(3) (THF)(4)Cl] (5), was isolated. 1-4 were characterized by NMR, IR and MS tec hniques as well as by X-ray structure determinations. According to them, I possesses a tetrahedrally coordinated Ga atom, at which two units of 1 are connected by hydrogen bridges to centrosymmetrical dimers. The In atoms in 2 have a trigonal-bipyramidal coordination sphere; the amine molecules occu py the apical positions. The central metal atom in 3 and the anion of 4 exh ibit trigonal-planar and distorted tetrahedral environments, respectively. The novel structural motif in 5 is the Cl- ion, only partly surrounded by L i+ ions in a strongly distorted trigonal-bipyramidal fashion. The dominatin g angle amounts to 165.2(2)degrees.