Preparation and Characterization of the Binary Group 13 Azides M(N3)3 and M(N3)3⋅CH3CN (M=Ga, In, Tl), [Ga(N3)5]2−, and [M(N3)6]3− (M=In, Tl)
作者:Ralf Haiges、Jerry A. Boatz、Jodi M. Williams、Karl O. Christe
DOI:10.1002/anie.201103101
日期:2011.9.12
caution: The use of fluoride starting materials and SO2 as a solvent yields neat triazides M(N3)3 (M=Ga, In, Tl), thus firmly establishing the existence of thallium triazide. In CH3CN, the new M(N3)3⋅CH3CN donor–acceptor adducts were obtained. Reactions of the triazides with tetraphenylphosphonium azide in CH3CN yields exclusively the novel [Ga(N3)5]2−, [In(N3)6]3− and [Tl(N3)6]3− anions (see picture, M green
In the TlF3-ZrF4 system, two phases have been detected : a cubic one formulated Tl0.67Zr0.33F3.33 and crystallizing with the Pm3m space group (a=4.061(1)A) and a rhombohedral one, TlZr3F15 (R3c space group with a=12.196(1)A, c=11.161(1)A). The structures have been refined using the Rietveld method. The refinement converges to RI=0.038 and 0.042 for Tl0.67Zr0.33F3.33 and TlZr3F15 respectively. The structures
diffraction for single crystals of Y and Gd and for powders using the Rietveld method for the other phases. The structure is isotypic with that of BiZr3F15 and corresponds to a three-dimensional network of corner-sharing octahedra and dodecahedra, in a 1:3 proportion (cationic sites 6a and 18e of the R3̄c space group). The cationicdistribution in these two sites depends on the size of the M3+ cation:
通过二元氟化物的直接反应制备一系列氟锆酸盐M Zr 3 F 15,涉及三价阳离子,其尺寸范围很广:In,Tl,Lu,Yb,Y,Gd,Eu和Pr(0.80Å
In the system MF3/AuF3 the structures of several yellow Tetrafluoroaurates (III) have been determinated. TlF2[AuF4] crystallizes tetragonal, space group P4(1)2(1)2 - D-4(4) (Nr.92) with a = 573.17(4) pm, c = 2780.4(3) pm, Z = 8; M2F[AuF4](5) (M = Bi, La) tetragonal, space group P4(1)2(1)2 - D-4(4) (Nr.92) with a = 822.89(5) pm, c = 2557.1(3) pm, Z = 4 (Bi); with a = 836.80(3) pm, c = 2602.2(2) pm, Z = 4 (La); Y2F[AuF4](5) monoclin, space group P2/n - C-2h(4) (Nr.13) with a = 1188.9(3)pm, b = 797.4(2)pm, c = 895.7(3)pm, beta = 89.18(3), Z = 4 and Sm[AuF4](3) trigonal, space group R(3) over bar c - D-3d(6) (Nr.1.67) with a = 1034.5(1) pm, c = 1614.1(3) pm, Z = 6. All these yellow crystals have been obtained by solid state reactions in autoclaves or sealed goldtubes.