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Synthesis and Crystal Structures of Bismuth Chalcogenolato Compounds Bi(SC6H5)3, Bi(SeC6H5)3, and Bi(S‐4‐CH3C6H4)3 Bismuth(III) acetate reacts with thiophenol in ethyl alcohol at 80 °C to yield Bi(SC6H5)3 ( 1 ). Slow cool down of the deep yellow mixture lead to the formation of orange crystals of 1 . The homotype phenylselenolato compound of bismuth Bi(SeC6H5)3 ( 2 ) has been prepared by the reaction of BiX3 (X = Cl, Br) with Se(C6H5)SiMe3 in diethyl ether. In the same way as Bi(SC6H5)3 ( 1 ) the reaction between bismuth(III) acetate and 4‐tolulenethiole results in red crystals of Bi(S‐4‐CH3C6H4)3 ( 3 ). In consideration of three longer Bi–E distances (intermolecular interactions, E = S; Se) the Bi(EPh)3 molecules form via face‐linked octahedra 1‐dimensional chains in the crystal lattice, while for 3 the 1‐dimensional chain is formed by face‐linked trigonal prisma. We reported herein the synthesis and structures of Bi(SC6H5)3 ( 1 ), Bi(SeC6H5)3 ( 2 ), and Bi(S‐4‐CH3C6H4)3 ( 3 ). 相似文献
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The intermetalloid clusters [M2Bi12]4+ (M = Ni, Rh) were synthesized as halogenido‐aluminates in Lewis‐acidic ionic liquids. The reaction of bismuth and NiCl2 in [BMIm]Cl · 5AlCl3 (BMIm = 1‐butyl‐3‐methylimidazolium) at 180 °C yielded black, triclinic (P1 ) crystals of [Ni2Bi12][AlCl4]3[Al2Cl7]. Black, monoclinic (P21/m) crystals of [Rh2Bi12][AlBr4]4 precipitated after dissolving the cluster salt Bi12–xRhX13–x (X = Cl, Br; 0 < x < 1) in [BMIm]Br·4.1AlBr3 at 140 °C. In the cationic cluster [Ni2Bi12]4+, the nickel atoms center two base‐sharing square antiprisms of bismuth atoms (symmetry close to D4h). The valence‐electron‐poorer rhodium‐containing cluster is a distorted variant of this motif: the terminating Bi4 rings are folded to bicyclic “butterflies“ and the central square splits into two dumbbells (symmetry close to D2h). DFT‐based calculations and real‐space bonding analyses place the intermetalloid units between a triple‐decker complex and a conjoined Wade‐Mingos cluster. 相似文献
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Bi9Rh2Br3, Bi9Rh2I3, and Bi9Ir2I3 – A New Structure Family of Quasi One‐dimensional Metals Bi9Rh2Br3, Bi9Rh2I3, and Bi9Ir2I3 were synthesized from the elements using niobium bromides or iodides as auxiliaries to modify the partial pressures in the course of the reaction. X‐ray diffraction on single crystals showed that the compounds are not isomorphous. However they have a common structural principle: strands of condensed [MBi8] polyhedra, which are separated by halide anions. The spatial arrangement of the [MBi1/1Bi7/2] strands differs with the combination of elements: In Bi9Rh2I3 (monoclinic, P21/m (no. 11), a = 775.6(1), b = 1374.9(2), c = 901.1(2) pm, β = 109.29(2)°) all strands are oriented parallel to each other. Bi9Rh2Br3 (monoclinic, P21/m (no. 11), a = 927.98(8), b = 1372.1(1), c = 1992.7(2) pm, β = 100.77(1)°) and Bi9Ir2I3 (orthorhombic, Pnma (no. 62), a = 2677.5(5), b = 1394.2(2), c = 967.6(1) pm) are ordered polytypes with two orientations changing in alternating layers of characteristic widths. The experimental proof of metallic conductivity in Bi9Ir2I3 supports the assumption of delocalised electrons inside the [MBi1/1Bi7/2] strands. The magnetic susceptibility of Bi9Rh2Br3 increases slowly with decreasing temperature and shows a local maximum at about 14 K. 相似文献
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Ag3Bi14Br21: a Subbromide with Bi24+ Dumbbells and Bi95+ Polyhedra – Synthesis, Crystal Structure and Chemical Bonding Black crystals of Ag3Bi14Br21 = (Bi95+)[Ag3Bi3Br153?](Bi2Br62?), the first argentiferous bismuth subhalide, were obtained from a stoichiometric melt of Ag, Bi, and BiBr3. The compound crystallizes in the monoclinic space group P21/m with lattice parameters a = 1277.78(5) pm, b = 1466.87(6) pm, c = 1342.62(5) pm, and β = 108.47(1)° at 110(5) K. In contrast to all other bismuth subhalides that contain an electron‐rich transition metal, the silver atoms are not bonded to bismuth atoms. Instead they are integrated into the anionic bromometallate network, which consists of [MBr6]‐octahedra (M = Ag, Bi) that share edges and vertices. These corrugated sheets alternate with tessellated layers formed by Bi95+ polycations and hitherto unknown (BiII2Br6)2? groups. The latter anions contain Bi24+ dumbbells (299 pm) and can be represented by the structured formula [Br2BiII(μ–Br)2BiIIBr2]2?. The multi‐center bonding within the Bi95+ cluster and the bent single‐bond in the Bi2 dumbbell can be visualized using the electron localization indicator (ELI‐D). 相似文献
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Low‐Temperature Topochemical Transformation of Bi13Pt3I7 into the New Layered Honeycomb Metal Bi12Pt3I5
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Martin Kaiser Bertold Rasche Dr. Anna Isaeva Prof. Dr. Michael Ruck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17152-17160
Ordered single‐crystals of the metallic subiodide Bi13Pt3I7 were grown and treated with n‐butyllithium. At 45 °C, complete pseudomorphosis to Bi12Pt3I5 was achieved within two days. The new compound is air‐stable and contains the same ${{{\hfill 2\atop \hfill \infty }}}$ [(PtBi8/2)3I]n+ honeycomb nets and iodide layers as the starting material Bi13Pt3I7, but does not include ${{{\hfill 1\atop \hfill \infty }}}$ [BiI2I4/2]? iodidobismuthate strands. Electron microscopy and X‐ray diffraction studies of solid intermediates visualize the process of the topochemical crystal‐to‐crystal transformation. In the electronic band structures of Bi13Pt3I7 and Bi12Pt3I5, the vicinities of the Fermi levels are dominated by the intermetallic fragments. Upon the transformation of Bi13Pt3I7 into Bi12Pt3I5, the intermetallic part is oxidized and the Fermi level is lowered by 0.16 eV. Whereas in Bi13Pt3I7 the intermetallic layers do not interact across the iodidobismuthate spacers (two‐dimensional metal), they couple in Bi12Pt3I5 and form a three‐dimensional metal. 相似文献
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Synthesis and Crystal Structure of Bi2ErO4I Bi2ErO4I was prepared by solid‐state reaction of stoichiometric mixture of BiOI, Bi2O3 and Er2O3. Bi2ErO4I is a new compound and the first bismuth rare earth oxide iodide. The crystal structure was determined by the Rietveldmethod (P4/mmm, a = 3,8896(6) Å, c = 9,554(2) Å, Z = 1). In this structure [M3O4]+‐layers are interleaved by single I–‐layers. Er and Bi atoms of Bi2ErO4I are 8‐coordinated. The structure can be derived from the LiBi3O4Cl2‐structure type. 相似文献
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Syntheses, Crystal Structures, and Triple Twinning of the Cluster Trimers Bi2[PtBi6Br12]3 and Bi2[PtBi6I12]3 Melting reactions of Bi with Pt and BiX3 (X = Br, I) yield shiny black, air insensitive crystals of the subhalides Bi2[PtBi6X12]. Bi2[PtBi6Br12]3 crystallizes in the monoclinic space group C2/m with lattice parameters a = 1617.6(2) pm, b = 1488.5(1) pm, c = 1752.4(2) pm, and β = 110.85(4)°. Bi2[PtBi6I12]3 adopts the triclinic space group with pseudo‐monoclinic lattice parameters a = 1711.2(2) pm, b = 1585.1(1) pm, c = 1865.7(2) pm, and α = 90°, β = 111.15(4)°, γ = 90°. The two homoeotypic compounds consist of cuboctahedral [Pt?IIBiII6X?I12]2? clusters that are concatenated into linear trimers by BiIII atoms. The ordered distribution of BiIII atoms destroys the inherent threefold rotation axes in the packing of cluster anions. As a consequence of the pseudosymmetry the crystals are triple twinned along [201]. Due to different orientations of the cluster trimers there are two BiII···X inter‐cluster bridges per BiII atom in Bi2[PtBi6Br12]3 but only one bridge in Bi2[PtBi6I12]3. The structure of the iodine compound can be deduced from the NaCl structure type, leaving 37 of 96 atomic positions unoccupied. The arrangement of the cuboctahedral clusters follows the motif of a body‐centered cubic packing. 相似文献
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Michael Ruck 《无机化学与普通化学杂志》2000,626(1):14-22
The Cluster Salts Bi14Si2MI12 (M = Rh, Ir): [Bi8Si2] and [MBi6I12] Building Groups in CsCl‐like Structure The reaction of bismuth and iridium with iodine in evacuated quartz ampoules at 1320 K yields black, air insensitive crystals of Bi14Si2IrI12. The silicon therein is abstracted from the ampoule material whereby the oxygen is gettered in BiOI. The synthesis of Bi14Si2RhI12 requires the addition of niobium, which gives NbOI2 with the oxygen originating from the SiO2. X‐ray diffraction on single crystals showed that the two isotypic compounds crystallize in the space groups P 4/m c c with a = 1018.3(1), c = 2020.1(4) pm for M = Ir, and a = 1019.0(1), c = 2018.7(4) pm for M = Rh. The crystal structures consist of two types of isolated clusters, which form a CsCl‐like packing. In the [MBi6I12] cuboctahedron the central transition metal atom is octahedrally surrounded by bismuth atoms, and the iodine atoms bridge the edges of the octahedron. The [Bi8Si2] polyhedron is a tetragonal antiprism of bismuth atoms of which square faces are capped by silicon atoms. Based on crystal chemistry and band structure calculations the compounds may be formulated as cluster salts [Bi8Si2]3+[MBi6I12]3–. Measurements of the electrical conductivity showed that Bi14Si2IrI12 is a semiconductor with a band gap of about 0.1 eV. A single unpaired electron out of 1903 electrons per formula causes paramagnetic behaviour that is superposed by strong diamagnetic contributions. 相似文献
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Falk Pabst Jen-Hui Chang Kati Finzel Miroslav Kohout Peer Schmidt Michael Ruck 《无机化学与普通化学杂志》2020,646(3):149-155
Black and irregularly shaped crystals of the bismuth-rich bromide Bi5Br4 were obtained as a by-product of the reaction of CsBr, Bi, and BiBr3. X-ray diffraction on a single-crystal revealed its orthorhombic structure with the space group Pmmn (no. 59) and lattice parameters a = 1800.0(2) pm, b = 1476.1(1) pm, and c = 924.5(2) pm at 296 K. The structure is composed of Bi82+ and Bi95+ polycations and bromidobismuthate(III) anions according to the structured formula Bi5Br4 = Bi20Br16 = Bi82+Bi95+[BiBr5]2–[Bi2Br11]5–. Bi5Br4 is the bismuth-richest among the bismuth subhalides containing isolated polycations. Extensive differential scanning calorimetry studies indicate that Bi5Br4 decomposes at 262 °C, i.e. one degree below the bismuth-rich eutectic at 263 °C. All attempts towards a rational synthesis yielded predominantly the neighboring phases BiBr and Bi6Br7. 相似文献
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Synthesis and Structures of Novel Ring Compounds of Bismuth with Tris(trimethylsilyl)silyl and ‐stannyl Substituents – [(Me3Si)3Si]4Bi4 and [(Me3Si)3Sn]6Bi8 A bicyclo[3.3.0]octane‐like core consisting of eight bismuth atoms is found in the novel octabismuthane Bi8[Sn(SiMe3)3]6. It is prepared like Bi4[Si(SiMe3)3]4 by reduction of BiBr3 with Li(thf)3E(SiMe3)3 (E = Si, Sn) together with (Me3Si)6E2. Both bismuth ring compounds have been characterized by single crystal X‐ray crystallography. 相似文献
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Awei Zhuang Jia‐Jun Li You‐Cheng Wang Xin Wen Yue Lin Prof. Bin Xiang Prof. Xiaoping Wang Prof. Jie Zeng 《Angewandte Chemie (International ed. in English)》2014,53(25):6425-6429
Bi2Se3 attracts intensive attention as a typical thermoelectric material and a promising topological insulator material. However, previously reported Bi2Se3 nanostructures are limited to nanoribbons and smooth nanoplates. Herein, we report the synthesis of spiral Bi2Se3 nanoplates and their screw‐dislocation‐driven (SDD) bidirectional growth process. Typical products showed a bipyramid‐like shape with two sets of centrosymmetric helical fringes on the top and bottom faces. Other evidence for the unique structure and growth mode include herringbone contours, spiral arms, and hollow cores. Through the manipulation of kinetic factors, including the precursor concentration, the pH value, and the amount of reductant, we were able to tune the supersaturation in the regime of SDD to layer‐by‐layer growth. Nanoplates with preliminary dislocations were discovered in samples with an appropriate supersaturation value and employed for investigation of the SDD growth process. 相似文献
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The viability of Lewis‐acid ionic liquids for the synthesis of low‐valent bismuth compounds is demonstrated. At room temperature, elemental bismuth and bismuth(III) cations synproportionate in the ionic liquid [BMIM]Cl/AlCl3 ([BMIM]+: 1‐n‐butyl‐3‐methylimidazolium) within minutes. The existence of bismuth polycations in the dark colored solution was proven by Raman spectroscopy. Dark‐red crystals of Bi5(AlCl4)3 were isolated from the ionic liquid and characterized by Raman spectroscopy and X‐ray crystallography (rhombohedral space‐group , a = 1187.1(2) pm, c = 3012.0(3) pm). The method allows the synthesis of bismuth cluster compounds under milder conditions than in high‐temperature melts and more conveniently and environmental friendly than in liquid SO2 with strongly oxidizing, toxic agents like SbF5 or AsF5. 相似文献