Aromaten-Komplexe mit Halbsandwich-Struktur: Die 1:1-Komplexe des Mesitylens mit SbCl3, SbBr3, BiCl3 und BiBr3

Arene Complexes with a Half-Sandwich Structure: The 1:1 Complexes of Mesitylene with SbCl₃, SbBr₃, BiCl₃, and BiBr₃ 1,3,5-Trimethylbenzene forms stable 1:1 complexes with SbCl₃, SbBr₃, BiCl₃, and BiBr₃ of the stoichiometry C₆H₃Me₃·EX₃ ( 1 – 4 ). According to the results of X-ray structure analyses of compounds 2 and 3 , one arene molecule is coordinated to each antimony or bismuth atom characterizing these adducts as half-sandwich species. To a good approximation the mesitylene molecules are centered over the metal atoms, but deviations from strict η⁶-hapticity are larger for antimony than for bismuth. – Despite some obvious analogies in many features of the structures, 2 and 3 are not isostructural. Differences appear with regard to the halogen bridging between the EX₃ moieties giving rise to the formation of two-dimensional networks (EX₃)_n covered above and below by mesitylene molecules. The structural and sequential principles of the layers differ in a characteristic way for 2 and 3 .     

Die Komplexe Pyren · 2 SbCl3 und Phenanthren - 2 SbBr3 Phasenverhalten,Präparation und Kristallstrukturen

Complexes Pyrene · 2 SbCl₃ and Phenanthrene · 2 SbBr₃: Phase Behaviour, Preparation, and Crystal Structures The melting diagrams of the systems pyrene-SbCl₃ and phenanthrene-SbBr₃ were studied by DTA. They are quasibinary and display one intermediate phase each of molar ratio 1:2 and melting congruently at 143 and 114°C, respectively. Their structures were determined by X-ray diffraction using single crystals obtained by sublimation. In pyrene. 2 SbCl₃ the two halogenide molecules are arranged on different sides, in phenanthrene - 2 SbBr₃ on the same side of the plane of the aromatic molecule. Sb ?π interactions lead to distances of the Sb atoms from this plane of 315 to 323 pm.     

Die Kristallstruktur und das Raman-Spektrum von SbCl3 · S8

Crystal Structure and Raman Spectrum of SbCl₃ · S₈ Contrary to literature data, the reaction of SbCl₅ with CS₂ at 5°C does not yield SbSCl₃ but SbCl₃ · S₈. At room temperature it already decomposes slowly to SbCl₃ and sulphur. The crystalline compound is built up from pyramidal SbCl₃ molecules and S₈ rings; pairs of SbCl₃ molecules form loosely associated dimeric units, furthermore there exist some relatively short Sb…?S contact distances. SbCl₃ · S₈ crystallizes in the space group P1 with the lattice constants a = 805, b = 867, c = 1073 pm, α = 94.9, β = 107.1 und γ = 111.6° (bei ?5°C). The crystal structure was determined with 2032 X-ray reflexions and was refined to a residual index of R = 0.028. The Raman spectrum is reported.     

Die Kristall- und MolekularStruktur von Antimontetrachloridazid (SbCl4N3)2

Antimony tetrachloride azide (SbCl₄N₃)₂ crystallizes in the monoclinic space group P2₁/n; the lattice parameters are: a = 8.051, b = 9.353, c = 10.124 Å; β = 93.75°; Z = 2. The crystal structure was solved with the aid of a Patterson synthesis and was refined by the method of least-squares to R = 4.9% for the 922 observed reflexions. The structure is built up from centrosymmetrical (SbCl₄N₃)₂ molecules (idealized point symmetry 2/m) which are arranged in the way of a body centered lattice. The linear azido groups are inclined against the planar (Sb–αN)₂ ring of the molecule by an angle of 24°. Each Sb atom is coordinated by two N and four Cl atoms in a distorted octahedral arrangement.     

Die Kristallstruktur von Antimontetrachlorid-cyanurat [SbCl4NCO]3

The Crystal Structure of Antimony Tetrachloride Cyanurate [SbCl₄NCO]₃ [SbCl₄NCO]₃ crystallizes in the hexagonal space group P6₃/m with two formula units per unit cell; the lattice parameters are a = 1167 and c = 995 pm. The crystal structure was solved with X-ray diffraction data by means of a Patterson and a Fourier Synthesis and was refined by the method of least-squares to a reliability index of R = 3.6% for the 863 observed reflexions. The structure consists of [SbCl₄NCO]₃ molecules having the point symmetry 6 . The molecule is a derivate of cyanuric acid in a way such that each Sb atom is bonded in chelate manner by one N and one O atom; together with 4 Cl atoms the antimony attains a distorted octahedral coordination. The packing density in the crystal is not optimal, there exist cavities.     

Darstellung,Eigenschaften und Schwingungsspektren von K[SbCl5N3], K[SbCl5NCO] und K[SbCl5CN]

Preparation, Properties and Vibrational Spectra of K[SbCl₅N₃], K[SbCl₅NCO] and K[SbCl₅CN]. KaN₃, KNCO and KCN react in liquid SO₂ with stoichiometric amounts of SbCl₅ yielding K[SbCl₅N₃] K[SbCl₅NCO], and K[SbCl₅CN], respectively. NaN₃ and SbCl₅ form Na[SbCl₅N₃] which contains impurities of Na[SbCl₆]. With more SbCl₅ (SbCl₄N₃)₂ is obtained from K[SbCl₅N₃] and (SbCl₄NCO)₂ from K[SbCl₅NCO], [BCl₂N₃]₃ is formed from K[SbCl₅N₃] and BCl₃. The vibrational spectra of the pentachloro-pseudohalo-antimonates can be assigned with a model of C_4v symmetry for the direct neighborhood of the Sb atoms.     

Bildungsweise und Schwingungsspektren von Antimontetrachlorid-isocyanat [SbCl4NCO]2 und -cyanurat [SbCl4NCO]3

Formation and Vibrational Spectra of Antimony Tetrachloride Isocyanate [SbCl₄NCO]₂ and Cyanurate [SbCl₄NCO]₃ [SbCl₄NCO]₂ was obtained from K[SbCl₅NCO] and SbCl₅ in liquid SO₂. In solution it is only stable at lower temperatures (?20°C); at room temperatures or above irreversible rearrangement to [SbCl₄NCO]₃ takes place. At higher temperatures this also occurs in the solid state, so that both compounds seen to have the same melting point of 208°C. In the molten state decomposition takes place, SbCl₃ being a main product. According to its i. r. and Raman spectrum, [SbCl₄NCO]₂ is an isocyanate with bridging N-atoms. I. r. and Raman spectrum of [SbCl₄NCO]₃ show it to be a derivative of cyanuric acid. Mass spectral data of both compounds are reported.     

Die Gasphasenintercalation von Graphit durch SbCl4F

Gas Phase Intercalation of Graphite by SbCl₄F Gas Phase Intercalation of Graphite by SbCl₄F using a two-zone technique is a method to prepare intercalation compounds of different stage index n in temperature range between 120 and 140°C. The reaction is a process of successive decrease of stage index. Increasing the reaction time, i. e. concentration, regions of pure stages alternate with two-phase regions. Intercalation compounds were characterized by X-ray technique, EPMA, and chemical methods. The compounds are stable in ordinary air, with aqueous HCl as well as KOH only pentavalent but not any trivalent antimony can be removed. The identity periods along c-axis in pure stages are I_c = 9.33 Å (n = 1), 12.72 Å (n = 2), 16.06 Å (n = 3) and 19.40 Å (n = 4). A (√7 × √ 7) 19.1° in-plane structure of intercalants was found. The uptake curve of mass with time reveals a discontinuity connected with formation of stage 2. Concave shape of curve during starting period at 120 and 125°C will be interpreted as a consequence of an induction time. From X-ray and EPMA studies it may be concluded that nucleation at the prismatic crystal edges controls the kinetics of reaction. Assuming a first order kinetics of filling the vacant sites, the same activation energy in case of formation of stage 1 and stage 2 have been determined approximately (97 and 102 kJ/mol).     

Solid State Structures of AsCl5 and SbCl5

Arsenic pentachloride has a trigonal bipyramidal structure in the solid state with As‐Cl_eq = 210.6, 211.9 pm, As‐Cl_ax= 220.7 pm, space group Pmmn, a = 706.2 (1); b = 760.3 (2), c = 623.3 (1) pm. Antimony pentachloride exists in two modifications: above −54.1 °C it is also trigonal bipyramidal with Sb‐Cl_eq = 227.0 and Sb‐Cl_ax = 233.3 pm, space group P6₃/mmc, a = 741.4 (1), c = 799.0(2)pm. Below −54.1 °C it changes reversibly into a double chlorine bridged dimer resulting in an edge shared double octahedral structure, space group P2₁/c, a = 952.4 (1), b = 1189.9 (1), c = 1219.7 (1) pm, β = 108, 27 (1): In presence of water the formation of AsCl₅ is hindered, two salts containing the octahedral anion AsCl₆⁻ have been isolated, [(H₅O₂⁺)₅AsCl₆⁻(Cl⁻)₄], space group C2/c, a= 1416.9 (2), b = 1316.6 (3), c = 1215.3 (2) pm, β; = 94.96 (1)°, and [(H₅O₂⁺)(AsCl₆⁻)·AsOCl₃], space group P2₁/n, a = 771.6 (3), b = 904.5 (3), c = 2140.7(2)pm, β = 100.21(1). The AsOCl₃ moiety in this compound appears as a monomer, in contrast to pure AsOCl₃, which is a doubly oxygen bridged dimer in the solid state.     

Mechanismus der Polymerisation von 1,3-Dioxolan mit (C2H5)3O-, SbCl6 und SbCl5

Ohne Zusammenfassung     

Die Kristallstruktur von [TeCl3(15-Krone-5)]SbCl6

The Crystal Structure of [TeCl₃(15-crown-5)]SbCl₆ The title compound is synthesized by the reaction of tellur tetrachloride, 15-crown-5 and antimony pentachloride in acetonitrile solution, forming colourless crystals, which were characterized by IR spectroscopy and an X-ray structure determination. Space group Pnma, Z = 4, 1966 observed unique reflections, R = 0.072, R_w = 0.052. The compound forms ions [TeCl₃(15-crown-5)]⁺ and SbCl₆^?; in the cation the tellurium atom is eightfold coordinated by the three chlorine atoms and the five oxygen atoms of the crownether molecule (Te? O bond lengths 266 and 279 pm).     

Darstellung,thermisches Verhalten und Kristallstruktur des Calciumarsenidchlorids Ca3AsCl3

Preparation, Thermal Stability, and Crystal Structure of the Calcium Arsenide Chloride Ca₃AsCl₃ CaAsCa₃AsCl₃ was prepared as a grayish white, microcrystalline powder by the reaction of Ca, As, and CaCl₂ in the molar ratio 3:2:3 and by the reaction of “Ca₃As₂” and CaCl₂ in the molar ratio 1:3. Colourless single crystals of the compound were obtained. Ca₃AsCl₃ begins to decompose reversibly at 1 025°C by forming the phase Ca_{2? x}As_{1? x}Cl_1+x with x = 0.1₃ and CaCl₂. Single crystal investigations show that Ca₃AsCl₃ is isotypic with Mg₃NF₃; see: “Inhaltsübersicht”.     

NQR-Untersuchungen an Addukten des SbCl3 und SbCl5. 35Cl- und 121,123Sb-NQR-spektroskopische Untersuchungen der Wechselwirkung zwischen SbCl3 bzw. SbCl5 und Phosphoryl- sowie Thiophosphorylchloriden

NQR Studies on Adducts of SbCl₃ and SbCl₅. ³⁵Cl- and ^121,123Sb-NQR Spectroscopic Studies of the Interaction between SbCl₃ or SbCl₅ and Phosphoryl or Thiophosphoryl Chlorides The complex formation between SbCl₃ and SbCl₅, respectively, and the chlorides POCl₃, P₂O₃Cl₄, and P₂OS₂Cl₄ has been studied by NQR spectroscopy. The formation of the adducts SbCl₃ · 2 POCl₃ and SbCl₅ · P₂OS₂Cl₄ has been proved. Based on its ³⁵Cl-NQR spectrum for the latter compound the constitution of a hexachloro antimonate P₂OS₂Cl₃⁺SbCl₆^? is assumed.     

Die Raman-Spektren von ZnTiO3 und CdTiO3

Raman Spectra of ZnTiO₃ and CdTiO₃ The laser Raman spectra of ZnTiO₃ and CdTiO₃ are recorded and discussed with the aid of a factor group analysis and in comparison with formerly reported IR data. The results allow a better insight into the vibrational behaviour of double oxides with ilmenite structure.     

Über die Darstellung von Arsendichloridtrifluorid,AsCl2F3

On the Preparation of Arsenic Dichloride Trifluoride, AsCl₂F₃ AsCl₂F₃ is prepared by pyrolysis of [AsCl₄]⁺ [AsF₆]^?. The vibrational spectra of the new low temperature compound are reported and the valence force constants are calculated. The formation of AsCl₂F₃ by ligand exchange reactions is discussed.     

Synthese,Kristallstrukturen und 121Sb-Mößbauer-Spektren von [SbBr3(15-Krone-5)], [SbBr2Me(15-Krone-5)] und [SbBr2Ph(15-Krone-5)]

Synthesis, Crystal Structure, and ¹²¹Sb-Mössbauer Spectra of [SbBr₃(15-Crown-5)], [SbBr₂Me(15-Crown-5)], and [SbBr₂Ph(15-Crown-5)] The compounds [SbBr₃(15-crown-5)] ( 1 ), [SbBr₂Me(15-crown-5)] ( 2 ), [SbBr₂Ph(15-crown-5)] ( 3 ), and [SbCl₂Me(15-crown-5)] ( 4 ) are formed by the reaction of 15-crown-5 with SbBr₃, SbBr₂Me, SbBr₂Ph, and SbCl₂Me, respectively, in toluene solution at ?40°C. The complexes were characterized by IR spectroscopy, ¹²¹Sb-Mössbauer spectroscopy, 1–3 as well as by X-ray structure determinations.

• 1 : Space group P2₁2₁2₁, Z = 4, 1735 observed, independent reflections, R = 0.050, Lattice dimensions at ?65°C: a = 787.03(7); b = 1313.0(2); c = 1619.3(2) pm.
• 2 : Space group Pca2₁, Z = 8, 2730 observed, independent reflections, R = 0.050, Lattice dimensions at ?65°C: a = 1308.2(2); b = 1611.8(2); c = 1640.5(3) pm.
• 3 : Space group P2₁/n, Z = 4,2458 observed, independent reflections, R = 0.040, Lattice dimensions at ?60°C: a = 900.3(3); b = 1390.6(6); c = 1618.5(7) pm, β = 96.32(3)°.

The complexes 1–3 have molecular structures, in which the antimony atoms are surrounded by the five oxygen atoms of the crown ether molecule and by three ligands Br₃, Br₂CH₃, Br₂Ph, respectively.     

Addukte schwefelhaltiger Heteroaromaten mit SbCl3 Untersuchungen zur Bildung und Kristallstruktur von 2,2′-Dithienyl · 2 SbCl3 und Benzo[b]thiophen · 2 SbCl3

Adducts of Sulfur-containing Hetero Aromates with SbCl₃: Studies on Formation and Crystal Structure of 2,2′-Dithienyl · 2 SbCl₃ and Benzo[b]thiophene · 2 SbCl₃ Whereas the system 2,2′-dithienyl—SbCl₃ because of irreversible thermal decomposition reactions could not be studied by DTA, this method applied to the system benzo[b]thiophene—SbCl₃ yielded a quasibinary behaviour and the existence of a compound benzo[b]thiophene · 2SbCl_3. melting congruently at 71.2°C. Crystals of this adduct and that of analogue composition 2,2′-dithienyl · 2SbCl₃ were obtained from solution. Their structures were determined by X-ray diffraction as those of bπ-v complexes. They are compared with other Menshutkin complexes. The π…?Sb interactions are indicated by distances between the planes of the planar hetero aromates and the Sb atoms located in a transoid way above both single rings of 316 (dithienyl adduct) and 325 pm (benzothiophene adduct). There is no particular coordinative bond formation by the S atoms. The intermolecular linking in the SbCl₃ partial structures is described.     

Die Kristallstruktur der Verbindung SbCl2F3

SbCl₂F₃ crystallizes in the monoclinic space group P 2₁/n (lattice parameters see above). The crystal structure has been determined by PATTERSON methods and refined three-dimensionally by the method of least squares. The structure is ionic and consists of tetrahedral SbCl cations and anions. In these anions pair of octahedrally coordinated Sb-atoms are linked by a fluorine bridge. A new interpretation of the IR and RAMAN spectra and a discussion of the character of the bonds of the fluorine atoms are given.