Water and oxygen sensitive compounds (tBu3SiEX2)2, tBu3SiEX2 Do and (tBu3Si)2EX (E = AI, Ga, In; X = (F), Cl, Br; Do = OR2, NR3) have been synthezised by reaction of EX3 with tBu3SiNa in the absence or presence of donors. In addition, (tBu3Si)AlBr2, (tBu3Si)2InF and tBu3SiInBr2 were prepared by reaction of AlBr3 with (tBu3Sij2Zn or of (tBu3Si)2In- In(Si/Bu3)2 with AgF2 and HBr, respectively. The adduct [tBu3SiAlBr2 · AlBr3 ·1/2MgBr2]2 is formed from AlBr3 and (tBu3Si)2Mg(THF)2. Thermal decomposition of the compounds in solution or in the gas phase leads to the formation of tBu3SiEX2 (from the dimers or the donor adducts) and of tBu3SiX. The Lewis acidity of tBu3SiEX2 against donors increases in the direction Do = Et2O < THF < NEtMe2. Dehalogenation of (tBu3Si)2ECl with tBu3SiNa(THF)2 in pentane at room temperature leads to clusters (tBu3Si)4Al2, (tBu3Si)3Ga2 •, (tBu3Si)4In2 and (tBu3Si)3Ga2Na(THF)3, reduction of tBu3SiGaCl2 with Na or K in heptane at 100°C to the tetrahedran (tBu3Si)4Ga4. The structures of (tBu3SiGaCl2)2, (tBu3Si)2GaCl, and [tBu3SiAlBr2 AlBr3 ·1/2MgBr2]2 have been determined by X-ray structure analysis.
Water- and oxygen-sensitive compounds R*EHal2•D, R*EHal2 and R*2EHal (R* = SitBu3; E = B, Al, Ga, In, TI; Hal = F, Cl, Br, I; D = OR2, NR3) have been synthesized by reaction of EHal3 with NaR* in the absence or presence of donors as well as by substitution of D, Hal or R* by other substituents, or by reaction of R*2E-ER*2 (E = Al, In) with I2, H2, AgF2 or HBr. Thermal decomposition of the compounds in solution or in the gas phase leads to elimination of D from R*EHal2•D, or of R*Hal from R*EHal2 and R*2EHal, respectively. The dihalides R*EHal2 act as Lewis acids with respect to donors OR2 or NR3 (formation of adducts R*EHal2•D), the monohalides R*2EHal as Lewis bases with respect to acceptors EHal3 (formation of R*2E+ EHal4 -). Dehalogenations of R*2EHal and R*EHal2 with alkali metals or NaR* leads to compounds R*4E2 (E = AI, In, Tl), R*3E2• (E = AI, Ga), R*4E3 • (E = Al, Ga), R*4E4 (E = AI, Ga), R*6Ga8, R*8In12, (R*2B- ), R*2A- , R*3Ga2 -, R*4Ga3 -, R*4Ga4 2-, R*4Tl3Cl, or R*6Tl6Cl2. The structures of R*BBr2•Py, R*AlBr2•NEtMe2, (R*AlClOBu)2, R*2BF as well as R*2ECl (E = B, Al, Ga, Tl) have been determined by X-ray structure analyses.