Darstellung und spektroskopische Charakterisierung von Carboxylatododecaboraten

Preparation and Spectroscopic Characterization of Carboxylatododecaborates The tetrabutylammonium salt (TBA)₂[B₁₂H₁₂]^2? reacts with formic, acetic, cyanoacetic, phenylacetic, propionic, butyric, and thioacetic acid at temperatures between 80 and 150°C forming the carboxylatododecaborates [(RC(O)O)_n? B₁₂H_{12? n}]^2?, n = 1, 2, [CH₃C(O)S? B₁₂H₁₁]^2?. The isolation of the pure compounds is achieved by ion exchange chromatography on diethylaminoethyl cellulose. In case of the dicarboxylatododecaborates beside the 1,7-isomer predominantly the 1,2-isomer, while 1,2-[(OH)C₆H₅CH₂C(O)O? B₁₂H₁₀]^2? is formed exclusively. The alcaline hydrolysis of [RC(O)O? B₁₂H₁₁]^2? and 1,2-[(OH)C₆H₅CH₂C(O)O? B₁₂H₁₀]^2? results in [(OH)? B₁₂H₁₁]^2? and 1,2-[(OH)₂? B₁₂H₁₀]^2?. All compounds are characterized by their ¹¹B-nmr, ¹³C-nmr and IR spectra. The ¹¹B-nmr signals are assigned by a sheme allowing to establish expected spectra.     

Darstellung und spektroskopische Charakterisierung von bindungsisomeren Halogenorhodanoosmaten(IV)

Preparation and Spectroscopic Characterization of Bond-Isomeric Halogenorhodanoosmates(IV) By oxidation of tr.-[OsCl₄BrI]^2? or tr.-[OsCl₄I₂]^2? with (SCN)₂ in CH₂Cl₂, by substitution of [OsCl₅I]^2? with SCN^? or [OsCl₅(NCS)]^2? with F^? in toluene and by reaction of [OsF₅Cl]^2? with (SCN)₂ in CH₂Cl₂ the following bondisomers are prepared: tr.-[OsF₄Cl(NCS)]^2?/tr.-[OsF₄Cl(SCN)]^2?, tr.-[OsFCl₄(NCS)]^2?/tr.-[OsFCl₄(SCN)]^2?, tr.-[OsCl₄Br(NCS)]^2?/tr.-[OsCl₄Br(SCN)]^2?, tr.-[OsCl₄I(NCS)]^2?/tr.-[OsCl₄I(SCN)]^2?,tr.-[OsCl₄(NCS)₂]^2?/tr.-[OsCl₄(NCS)(SCN) ]^2?/tr.-[OsCl₄(SCN)₂]^2?, [OsBr₅(NCS)]^2?/[OsBr₅(SCN)]^2? and tr.-[OsBr₄(NCS)(SCN)]^2?. All complexes are isolated as pure compounds by ion exchange chromatography on DEAE-cellulose. In the IR and Raman spectra ν_CN(S), ν_CS(N) and δ_NCS are found at higher wave numbers than ν_CN(N), ν_CS(S) and δ_SCN. According to spin orbit coupling and to lowered symmetry (D_4h, C_4v) the splitted intraconfigurational transitions are observed at 10 K as weak bands in the regions 600, 1000, 2000 nm. The O? O transitions are calculated from vibrational fine structure and in some cases are confirmed by electronic Raman bands with the same frequencies. The energy niveaus deduced with ζ(Os^IV) = 3200 cm^?1 and the calculated Racah parameters B are in good agreement with the barycenters of the observed multiplets for D_4h and C_4v symmetry.     

Darstellung und spektroskopische Charakterisierung von Bindungsisomeren Halogenoselenocyanatoosmaten(IV)

Preparation and Spectroscopic Characterization of Bondisomeric Halogenoselenocyanatoosmates (IV) The new compounds [OsCl₅(NCSe)]^2?, [OsCl₅(SeCN)]^2?, tr.-[OsCl₄(NCSe)(SeCN)]^2?, tr.-[OsCl₄I(NCSe)]^2? and tr.-[OsCl₄I(SeCN)]^2? are prepared from [OsCl₅I]^2? and tr.-[OsCl₄I₂]^2? by oxidative ligand exchange with (SeCN)₂ or by reaction with suspended Pb(SeCN)₂ in CH₂Cl₂ and isolated by ion exchange chromatography on DEAE cellulose. The bondisomers are significantly distinguished by the frequencies of innerligand vibrations: ν_CN(Se), ν_CN(N), ν_CSe(N) > ν_CSe(Se), δ_NCSe >, δ_SeCN. The electronic spectra measured at 10 K on the solid salts exhibit in the region 450–650 nm intensive Se → Os and N → Os charge transfer bands. Essentially weaker intraconfigurational transitions (t) are observed near to 2000 and 1000 nm, splitted by lowered symmetry (C_4v) and spin orbit coupling. Only some of the 0–0-transitions may be assigned by measuring electronic Raman bands with the same frequencies.     

Darstellung und spektroskopische Eigenschaften von Nitridophthalocyaninatorhenium(V)

Preparation and Spectroscopical Properties of Nitridophthalocyaninatorhenium(V) Nitridophthalocyaninatorhenium(V) ([ReNPc^2?]) is prepared by the reaction of dirheniumheptoxide with ammoniumiodide in molten 1,2-dicyano-benzene. The diamagnetic complex is chemically und thermically extremely stable. In the Uv-vis spectra the typical π-π*-transitions of the Pc^2? ligand are observed. Extra bands in the solid state spectrum are due to strong excitonic coupling of ca. 2.8 kK. In the resonance Raman spectra the intensity of the Re≡N stretching vibration (v(Re≡N)) at 969 cm^?1 is selectively enhanced by laser excitations above 19.0 kK. v(Re≡N) is a dominant m.i.r. absorption at 976 cm^?1.     

Darstellung und spektroskopische Charakterisierung von Di(acido)phthalocyaninatorhodaten(III)

Preparation and Spectroscopical Characterization of Di(acido)phthalocyaninatorhodates(III) Triethylendiaminorhodiumiodide reacts quickly and completely with boiling phthalodinitrile precipitating ?rhodiumphthalocyanine”?, which is purified and dissolved in alkaline media as di(hydroxo)phthalocyaninatorhodate(III). Acidification in the presence of halides or pseudohalides yields less soluble acidophthalocyaninatorhodium reacting with tetra-n-butyl-ammonium(pseudo)halide to give (blue)green tetra-n-butyl-ammoniumdi(acido)phthalocyaninatorhodate(III), (ⁿBu₄N)[Rh(X)₂Pc^2?] (X = Cl, Br, I, N₃, CN, NCO, SCN, SeCN). The asym. Rh? X-stretching vibration (v_as(RhX)) is observed in the f.i.r. at 290 (X = Cl), 233 (Br), 205 (I), 366 (N₃), 347 (CN), 351 (NCO), 257 (SCN) and 214 cm^?1 (SeCN). v_s(RhI) is the only sym. Rh? X-stretching vibration excited at 131 cm^?1 in the Raman spectrum. The m.i.r. and resonance Raman spectra are typical for hexacoordinated phthalocyaninatometalates(III). The influence of the axial ligands is very small. The frequency of the stretching vibrations of the pseudohalo-ligands are as expected (in the case of the ambident ligands the bonding atom is named first): v_as(NN) at 2006 and v_s(NN) at 1270 cm^?1 (N₃); v_as(CN) at 2126 (CN), 2153 (NCO), 2110 (SCN) and 2116 cm^?1 (SeCN). The characteristic π–π*-transitions of the Pc^2?-ligand dominate the UV-vis spectra. The splitting of the Q and N region is discussed and the weak absorbance at ca. 22 kK is assigned to a n–π*-transition.     

Darstellung und spektroskopische Charakterisierung von bindungsisomeren Halogenoselenocyanato-Osmaten(IV) und -Rhenaten(IV)

Preparation and Spectroscopic Characterization of Bond Isomeric Halogenoselenocyanato-Osmates(IV) and -Rhenates(IV) By oxidative ligand exchange of appropriate chloro-iodo complexes of Os^IV or Re^IV with (SeCN)₂ in CH₂Cl₂ or by heterogeneous reaction with Pb(SeCN)₂ or AgSeCN in CH₂Cl₂ the new complexes cis-[OsCl₄(NCSe)(SeCN)]^2?, tr.-[OsCl₄Br(NCSe)]^2?, tr.-[OsCl₄Br(SeCN)]^2?, [ReCl₅(NCSe)]^2?, [ReCl₅(SeCN)]^2?, tr.-[ReCl₄I(NCSe)]^2?, tr.?[ReCl₄(NCSe)(SeCN)]^2? and tr.?[ReCl₄(NCSe)₂]^2? are formed and isolated as pure compounds by ion exchange chromatography on DEAE-cellulose. The bond isomers are significantly distinguished by the frequencies of innerligand vibrations: n?_CN(Se) > n?_CN(N); n?_CSe(N) > n?_CSe(Se); δ_NCSe > δ_SeCN. The electronic spectra (10 K) of the solid salts reveal a bathochromic shift for the charge transfer bands of the Se isomers as compared with the corresponding N isomers. The intra-configurational transitions are observed for the Os^IV complexes at 600 to 2400 and for the Re^IV complexes at 500 to 1600 nm. The ⁷⁷Se nmr signals of the Os^IV bond isomers are registrated for Se binding in the region 970 to 1040 ppm, for N coordination downfield at 1540 to 1640 ppm.     

Darstellung,Kristallstruktur und spektroskopische Charakterisierung von P4O6Se3

Synthesis, Crystal Structure, and Spectroscopic Characterization of P₄O₆Se₃ P₄O₆Se₃ has been prepared for the first time as a pure substance by photochemical selenation of P₄O₆ with red selenium. The compound crystallizes in a monoclinic system with space group P2₁/a (a = 973.6(2); b = 846.9(2); c = 1277.7(3) pm; β = 90.56(2)°; Z = 4; 1358 diffractometer data; R₁ = 0.044; wR² = 0.099). Bond lengths and angles within the molecule as well as the arrangement of the molecules within the crystal are discussed; vibrational (IR and Raman) and ³¹P-n.m.r. (solution) data are given.     

Darstellung von Fluorjodsilanen (über Halogenaustauschreaktionen) und ihre spektroskopische Charakterisierung. Spektren von SiBrCl2F und SiBr2ClF

Zusammenfassung Durch Br/J-Austauschreaktionen entstehen aus den entsprechenden Bromfluorsilanen und HSiJ₃ die bisher unbekannten Fluorjodsilane SiFCl₂J, SiFClJ₂, SiFBr₂J SiFBrJ₂ und SiF₂BrJ sowie auch SiFJ₃ und SiF₂J₂. Die¹⁹F-NMR-Parameter und die zugeordneten Schwingungsspektren dieser Verbindungen sowie von SiFCl₂Br und SiFClBr₂ werden angegeben und diskutiert.

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Synthesis of fluoroiodosilanes by halogen exchange reactions and their spectroscopic characterization. spectra of SiBrCl₂F and SiBr₂ClF

Br/I-exchange reactions between some bromofluorosilanes and HSiI₃ lead to the hitherto unknown fluoroiodosilanes SiFCl₂I, SiFClI₂, SiFBr₂I SiFBrI₂, and SiF₂BrI as well as SiFI₃ and SiF₂I₂. The¹⁹F-NMR data and vibrational spectra (including assignments) of these compounds and of SiFCl₂Br and SiFClBr₂ are reported and discussed.

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Herrn Prof. Dr.Harald Schäfer zum 60. Geburtstag gewidmet.     

Darstellung und Charakterisierung von Bindungsisomeren Bromorhodanorhenaten(IV)

Preparation and characterization of bondisomeric bromorhodanorhenates(IV) The new compounds [ReBr₅(SCN)]^2?, [ReBr₅(NCS)]^2?, cis/tr.-[ReBr₄(NCS)(SCN)]^2?, cis-[ReBr₄(NCS)₂]^2?, mer-[ReBr₃(NCS)₃]^2? are prepared from [ReBr₆]^2? by ligand exchange with NaSCN, KSCN, or (SCN)₂ in organic solvents and isolated by ion exchange chromatography on DEAE cellulose. The bondisomers are significantly distinguished by the frequencies of inner ligand vibrations: v_CN(S) > v_CN(N), v_CS(N) > v_CS(S), δ_NCS δ_SCN. The electronic absorption spectra measured at 10 K exhibit in the region 5700 to 15300 cm^?1 all intraconfigurational transitions (t_2g³) splitted into 8 Kramers doublets by lowered symmetry (C_4v, C_2v, C_s) and spin orbit coupling. The O–O-transitions are deduced form vibrational fine structure and confirmed by electronic Raman bands in some cases. The magnetic moments are in the range of 3.0 to 3.9 B.M.     

Darstellung und spektroskopische charakterisierung von mer-trihalogeno-carbonyl-oxalato-osmaten(III)

Upon treatment of trans-[OsX₄(CO)₂]^? or [OsX₅(CO)]^2? with oxalate in aqueous solution new complexes of the type mer-[OsX₃(CO)ox]^2? (X  Cl, Br, I) are formed. The IR and Ra spectra are assigned according to point group C_s. In the UV/VIS spectra, recorded at 10 K, charge transfer transitions from ligand levels, splitted by spin-orbit coupling, (π + σ)t_1u(X) and πt_2u(X) to t_2g(Os³⁺) are observed. Two weak bands with vibrational fine structure in the NIR region are assigned to intraconfigurational transitions within the ground term of osmium(III). The assignment is confirmed by bands of the same frequency observed in the electronic Raman spectrum.     

Darstellung und Charakterisierung von Lithiumhydrogenphthalocyanin

tPreparation and Characterization of Lithiumhydrogenphthalocyanine Lithiumhydrogenphthalocyanine is obtained by the thermal decomposition of tetraalkylammoniumlithiumphthalocyanines as monoclinic blue needles (a = 19.081(9), b = 4,996(3), c = 14.437(7) Å; β = 119.64(4)° (from powder diffraction data)). The properties, IR and UV-VIS spectra are discussed.     

Darstellung und spektroskopische Untersuchungen von Trivinyl- und Triallyl-fluorsilan

Preparation and Spectroscopical Investigations of Trivinyl- and Triallylfluorosilane Trivinyl- and Triallylfluorosilane were prepared. The i.r. and Raman spectra have been recorded. The discussion of intra- and intermolecular interactions is based on the spectroscopic data.     

Darstellung,Kristallstruktur und spektroskopische Charakterisierung von [(H3C)3Si]NH(BCl2)

Preparation, Crystal Structure, and Spectroscopic Characterization of [(H₃C)₃Si]NH(BCl₂) [(H₃C)₃Si]NH(BCl₂) is formed during the reaction of boron trichloride with hexamethyldisilazane at low temperatures. The compound crystallizes monoclinic in space group P2₁/c with a = 953.8(2) pm, b = 1059.9(1) pm, c = 867.4(1) pm, β = 99.40(2)°; Z = 4. According to the single crystal X-ray diffraction analysis (1275 symmetry independent reflections, R = 0.040), [(H₃C)₃Si]NH(BCl₂) exists as a dimer, in the crystal. The dimers have site symmetry C_i and, within the margins of error of the structure determination, point symmetry C_2h. A characteristic feature is a planar, almost square B–N–B–N four-membered ring with the trimethylsilyl groups in trans position. The compound has been characterised by MS-, ¹H-, ¹³C-, ¹¹B-, and ²⁹Si-NMR-spectroscopy.     

Darstellung und Charakterisierung von Tetrakis(Chloro-Bromo)-Oxalato-Osmaten(IV)

Preparation and Characterization of Tetrakis(chloro-bromo) Oxalatoosmates(IV) On treatment of [OsBr₄ox]^2? with Cl^? the yellow to orange coloured complexes [OsCl_nBr_4?nox]^2?, n = 1, 2, 3, are formed. The separation of geometric isomers is difficult but possible by ion exchange chromatography on diethylaminoethyl cellulose. The 10 K absorption spectra show in the UV/VIS region intensive Br←Os and Cl←Os charge transfer bands and in the NIR weak intraconfigurational transitions splitted by spin-orbit coupling and lowered symmetry into 5 components. A very weak spin-forbidden d—d-transition at about 600 nm is improved as a luminescence absorption band in the Raman spectrum.     

Darstellung und Charakterisierung von amphoteren Polystyrol-Latexverbindungen

Ohne Zusammenfassung     

Untersuchungen über N-Methoxyguanidin 1. Darstellung und spektroskopische Charakterisierung

Studies on N-Methoxyguanidine. 1. Synthesis and Spectroscopic Characterization The hitherto unknown title compound has been isolated as a free base. The infrared, nuclear magnetic resonance, and mass spectra are reported. The amino protones are involved in rapid interchange processes. The activation values of the interchanges have been approximately determined from temperature dependent ¹H-n.m.r. experiments. The related tautomeric structures are discussed.     

Darstellung und spektroskopische Charakterisierung von Perfluor(isopropyl)trifluoracetylperoxid (CF3)2C(F)OOC(O)CF3

Preparation and Spectroscopic Characterization of Perfluoro(isopropyl)-trifluoroacetylperoxide (CF₃)₂C(F)OOC(O)CF₃ The reaction of perfluoroacetone (CF₃)₂CO with OF₂ in a ratio 2 : 1 yields Perfluoro(isopropyl)-trifluoroacetylperoxide (CF₃)₂C(F)OOC(O)CF₃. The reaction only occurs under CsF-catalysis. (CF₃)₂C(F)OOC(O)CF₃ is characterized by vibrational, nmr and mass spectra. Using an excess of OF₂ does not give any stable product.     

Darstellung und spektroskopische Charakterisierung von Fluortrichlor-arsoniumhexafluoroarsenat,AsFCl3+AsF6−

Preparation and Spectroscopic Characterization of Fluorotrichloroarsonium Hexafluoroarsenate, AsFCl₃⁺AsF₆^? The mixed halide pniktide cation AsFCl₃⁺ is prepared by oxidative fluorination of AsCl₃ with XeF⁺ AsF₆^?. AsFCl₃⁺ AsF₆^? is characterized by IR, Raman, and ¹⁹F-NMR spectroscopy.