IR-Spektren von N-Tri-[methyl(d 3)]- und N-Trimethyl-borazolderivaten

Zusammenfassung Zuordnungen für die IR-Spektren von N-Tri-[methyl(d ₃)]-B-trichlor- und N-Tri-[methyl(d ₃)]-B-triamino-borazol werden angegeben.Mit 3 Abbildungen     

Darstellung von kristallwasserfreien Boraten aus Tris(methoxy)boran und Diskussion des Reaktionsweges

Preparation of Anhydrous Borates from Tris(methoxy)borane and Discussion of the Reaction Path Borates and polyborates of lithium, potassium, rubidium, calcium, and strontium free from water of crystallization are prepared. The infrared, Raman, ¹H- and ¹¹B nuclear magnetic resonance spectra suggest that the slowest step in the hydrolysis of tris(methoxy) borane in the presence of metal alkoxides in organic solvents may be expressed by the equation [ROB(OH)₃]^? + ROB(OH)₂ ? [RO(HO)₂BOB(OR)(OH)]^? + H₂O (R = CH₃ or H). From this alkylated diborate triborates, tetraborates, and pentaborates are then formed by a similar condensation sequence.     

Die IR-Spektren von [Cr(O2)2(NH3)3] und K3[Cr(O2)2(CN)3]

The infrared spectra of the title compounds are reported and discussed. The influence of the peroxide groups on the bond properties of the other ligands and some characteristics of the metal—peroxide interactions are analyzed.     

Die IR-Spektren von Furan-, Pyrrol- und Thiophenderivaten

Ohne Zusammenfassung     

IR-Spektren von 2,4,6-Tris(dimethylamino)- und 2,4,6-Tris[dimethylamino(d6)]-borazinderivaten

Zusammenfassung Der Vergleich der Spektren von B-Dimethylaminoborazinen mit jenen der entsprechenden B-Hexadeuterodimethylaminoborazine zeigt starke Wechselwirkungen zwischen BN- und CH₃-Schwingungen, die ebenso wie in anderen N- und O-Methylborazinen zu einer Frequenzminderung der B–N-Hauptbande führen.

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By comparison of the IR-spectra of B-dimethylaminoborazines with those of their hexadeuterodimethylamino analogous shows strong interactions of BN and CH₃-frequencies. BN frequencies are decreased like in other O- and N-methylborazines.

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Mit 2 Abbildungen     

Die IR-Spektren von Kobalt-, Nickel- und Zink-Orthovanadat

Infrared spectra of crystalline Co₃(VO₄)₂, Ni₃(VO₄)₂ and Zn₃(VO₄)₂ as well as the laser-Raman spectrum of the last mentioned compound are reported and discussed. A series of solid solutions of the type (Zn/Ni)₃(VO₄)₂ have also been prepared and investigated, in order to obtain a wider insight into the spectroscopic behaviour of this class of compounds in the 500-250 cm^–1 region. Comparisons with the formerly investigated isotypic Mg₃(VO₄)₂ allows to confirm some of the earlier statements and assignments in the light of additional experimental information.

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26. Mitt. der Reihe Orthovanadate und verwandte Verbindungen. 25. Mitt.:E. J. Baran, J. Mol. Struct., im Durck; 24. Mitt.:E. J. Baran undI. L. Botto; J. inorg. nucl. Chem., im Druck; 23. Mitt:M. E. Escobar undE. J. Baran, Z. anorg. allg. Chem., in Druck.     

Darstellung und Struktur von tert-Butyl(tert-butylamino)-[tris(tert-butyloxy)silylthio]boran

Formation and Structure of tert-Butyl(tert-butylamino) [tris(tert-butyloxy)silylthio]-borane The smooth addition of the SH bond of (tBuO)₃SiSH to the BN bond of tBuB?NtBu gives the title compound, which crystallizes in the triclinic system, space group P1 , with an unexpectedly short BN bond, d(BN) = 137 pm, in a Z configuration.     

Die IR-Spektren von Derivaten der Cyclohexadienone

Zusammenfassung Aus den IR-Spektren der untersuchten Verbindungen können die Einflüsse benachbarter Substituenten auf die Schwingungen der Carbonylgruppe studiert werden; ebenso werden die Substituenteneinflüsse auf die Schwingungen des quartären Kohlenstoffatoms in Cyclohexadienonen untersucht. Es wird weiter gezeigt, daß auch beim Ringsystem der Cyclohexadienone aus den -Frequenzen Rückschlüsse auf den Substitutionstyp am Ring gezogen werden können, wie dies von den aromatischen Ringsystemen her bekannt ist. Schließlich wird die Verschiebung der -C=O , -ungesättigter Ketone durch eine , -Doppelbindung untersucht, deren Ausmaß in der bisherigen Literatur allgemein als zu gering angenommen worden ist.Mit 1 Abbildung     

Die Brauchbarkeit von Debye-Scherrer Diagrammen und IR-Spektren zum Nachweis von einigen Sterinen und ihrer Digitonide

Ohne Zusammenfassung     

Die Aufnahme der IR-Spektren von Polymeren

Ohne Zusammenfassung     

(BO)-Banden in den IR-Spektren von Deuteroalkoxyboranen und Halogenalkoxyboranen

Zusammenfassung Anhand der IR-Spektren von Deuteroalkoxy-und Halogenalkoxyboranen wird gezeigt, daß in Alkoxyboranen Kopplungen zwischen (BO)-Valenz- und (CH)-Deformationsschwingungen bestehen.

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(BO) bands in the IR spectra of deutero alkoxyboranes and halogeno alkoxyboranes

Coupling of (BO)stretching and (CH)deformation modes in alkoxyboranes is shown by studying the IR spectra of deuteroalkoxy-and halogenalkoxy-boranes.

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Die Einwirkung von Ammoniumfluorid auf Scandium: Synthese und Kristallstrukturen von (NH4)3[ScF6] und [Cu(NH3)4]3[ScF6]2

Action of Ammonium Fluoride on Scandium: Synthesis and Crystal Structures of (NH₄)₃[ScF₆] and [Cu(NH₃)₄]₃[ScF₆]₂ The action of (NH₄)F on scandium in copper ampoules yields either (NH₄)₃[ScF₆] or ScF₃ and a small quantity of [Cu(NH₃)₄]₃[ScF₆]₂, respectively, depending upon the molar ratio of the educts (NH₄)F : Sc (6 : 1 and 4 : 1, respectively) and temperature. (NH₄)₃[ScF₆] crystallizes with the cryolite type of structure: monoclinic, P2₁/n, Z = 2; a = 650.0(2); b = 651.4(2); c = 949.0(2) pm; β = 90.40(2)°, [Cu(NH₃)₄]₃[ScF₆]₂ is triclinic, P‐1, Z = 1; a = 821.1(2); b = 821.2(2); c = 822.7(2) pm; α = 90.04(3); β = 90.00(3); γ = 90.16(3)°. In its chemical behaviour against (NH₄)F, scandium parallels aluminium rather than gallium.     

Phosphaniminato-Komplexe von Niob und Tantal. Die Kristallstrukturen von [NbCl4(NPiPr3)(CH3CN)], [NbCl3(NPiPr3)2], [TaCl4(NPiPr3)]2 und [TaCl3(NPiPr3)2]

Phosphorane Iminato Complexes of Niobium and Tantalum. Crystal Structures of [NbCl₄(NPⁱPr₃)(CH₃CN)], [NbCl₃(NPⁱPr₃)₂], [TaCl₄(NPⁱPr₃)]₂, and [TaCl₃(NPⁱPr₃)₂] The title compounds have been prepared from the pentachlorides of niobium and tantalum with the silylated phosphorane imine Me₃SiNPⁱPr₃. They are characterized by IR spectroscopy and crystal structure determinations. NbCl₄(NPⁱPr₃)(CH₃CN)] . Space group Pna2₁, Z = 4, 2102 observed unique reflections, R = 0.022. Lattice dimensions at ?50°C: a = 1627.2, b = 876.3, c = 1335.3 pm. The compound forms monomeric molecules with the acetonitrile molecule in trans position to the phosphorane iminato group. This group shows a short NbN distance of 178.2 pm with a NbNP bond angle of 165.2°. [NbCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 2534 observed unique reflections, R = 0.046. Lattice dimensions at 20°C: a = 1302.65, b = 1321.69, c = 1672.04 pm, β = 111.713°. The compound forms monomeric molecules with a distorted bipyramidal surrounding of the niobium atom and equatorially arranged phosphorane iminato groups. [TaCl₄(NPⁱPr₃)]₂ . Space group Pbca, Z = 4, 1537 observed unique reflections, R = 0.037. Lattice dimensions at ?40°C: a = 1420.6, b = 1483.9, c = 1622.0 pm. The compound forms centrosymmetric dimeric molecules with dissimilarly long Ta₂Cl₂ bridges and equatorially arranged phosphorane iminato groups. [TaCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 5737 observed unique reflections, R = 0.039. Lattice dimensions at ?50°C: a = 1303.9, b = 1327.2, c = 1682.1 pm, β = 111,92°. The compound is isotypical with the corresponding niobium compound.     

Reaktionen von Sauerstoff- bzw. Schwefel-Heterocyclen mit Natrium und Dichlor(diisopropylamino)boran

Reactions of Oxygen- and Sulfur-Heterocycles with Sodium and Dichloro(diisopropylamino)borane Thiophene reacts with sodium and dichloro(diisopropylamino)borane to give 2,4-Bis-(diisopropylamino)-1,3,2,4-dithiadiboretane ( a ). In the reactions of dibenzothiophene, dibenzofurane, and xanthene, resp., with sodium and dichloro(diisopropylamino)borane one side of the hetero-bridge is split. Thus one obtains the amino(phenylthio)borane 1 and the amino(phenoxy)- boranes 2 and 3 . The compounds are characterized analytically and spectroscopically (MS; NMR: ¹H, ¹¹B, ¹³C).     

Phosphaniminato-Komplexe von Cobalt und Zink mit Heterocubanstruktur. Die Kristallstrukturen von [CoI(NPMe3)]4 und [ZnI(NPMe3)]4

Phosphoraneiminato Complexes of Cobalt and Zinc with Heterocubane Structure. Crystal Structures of [CoI(NPMe₃)]₄ and [ZnI(NPMe₃)]₄ The title compounds have been prepared from CoI₂ and ZnI₂, respectively, and Me₃SiNPMe₃ by fusion reactions at 180°C in the presence of sodium fluoride. They crystallize from dichloromethane as dark green (Co) or colourless (Zn) single crystals including three molecules CH₂Cl₂ per formula unit, which were characterized by crystal structure determinations. [CoI(NPMe₃)]₄ · 3 CH₂Cl₂: Space group P3m1, Z = 2, structure solution with 2376 independent reflections, R = 0.033. Lattice dimensions at ?50°C: a = b = 1455.8, c = 1270.5 pm. [ZnI(NPMe₃)]₄ · 3 CH₂Cl₂: Space group P3m1, Z = 2, structure solution with 2197 independent reflections, R = 0.043. Lattice dimensions at ?60°C: a = b = 1454.9, c = 1270.5 pm. Both complexes are isostructural with one another. They form heterocubane structures in which the metal atoms are linked via μ₃-N-bridges of the phosphoraneiminato groups with M₄N₄ bridge-type bond angles close to 90°.     

Struktur und Eigenschaften von Doppelhalogeniden von substituiertem Ammonium und Quecksilber(II). VI [1]. Die Kristallstruktur von (CH3NH3)2HgBr4 und (CH3NH3)2HgI4

Structure and Properties of Double Halogenides of Substituted Ammonium and Mercury(II). VI. Crystal Structure of (CH₃NH₃)₂HgBr₄ and (CH₃NH₃)₂HgI₄ The compounds (CH₃NH₃)₂HgBr₄ and (CH₃NH₃)₂HgI₄ were prepared from stoichiometric mixtures of the methylammonium halogenides and the mercury(II) halogenides in methanol by evaporation. X-ray structure determination revealed for (CH₃NH₃)₂HgBr₄ monoclinic symmetry, space group P2₁/c and orthorhombic symmetry, space group Pbca for (CH₃NH₃)₂HgI₄. Both compounds are built from isolated, slightly deformed tetrahedra. The Hg? Br distances range from 2.586(3) Å to 2.598(2) Å, the Br? Hg? Br angles from 105.36(8)° to 112.26(8)°. The observed distances in the HgI₄ tetrahedra are in the range 2.751(1) and 2.803(1) Å, the I? Hg? I angles between 106.25(3)° and 115.68(4)°. The tetrahedra are linked together by hydrogen bonds between the methylammonium group and the halogen atoms.     

Die Schwingungsspektren von Ca3(VO4)2 und Ca3(AsO4)2[l]

Inhaltsübersicht. Die IR- und Raman-Spektren von Ca₃(VO₄)₂ wurden aufgenommen und an Hand der “Site-Symmetrie”-Regeln interpretiert. Auch das IR-Spektrum des isostrukturellen Ca₃(AsO₄)₂ wurde zu Vergleichszwecken untersucht. The Vibrational Spectra of Ca₃(VO₄)₂ and Ca₃(AsO₄)₂ Abstract. The infrared and Raman spectra of Ca₃(VO₄)₂ are reported and discussed with the aid of the “site symmetry” rules. For comparative purposes, the i.r. spectrum of the isostructural Ca₃(AsO₄)₂ has been also analyzed.