Antimon(III) und Arsen(III)

Ohne Zusammenfassung     

Oxinkomplexe von Gold(III) und Titan(III)

Ohne Zusammenfassung     

Komplexverbindungen von Pr(III) und Nd(III) mit o-Hydroxybenzohydrazid und Salicylaldehyd

Reaction of Pr(III) and Nd(III) with o-hydroxybenzohydrazide yields either tris-(o-hydroxybenzohydrazidato) compounds of typeM(o-Bh)₃·3 H₂O, whereM(III) is Pr or Nd, or tris-(salicyladehydato) compounds: Pr(o-Bh)₃(Sald)₃· 4 H₂O, Pr(o-Bh)₆(Sald)₃ and Nd(o-Bh)₃(Sald)₃·2 H₂O, Nd(o-Bh)₆(Sald)₃. The metal to ligand ratio in the compounds formed with neutral o-hydroxybenzohydrazide was either 1∶3 or 1∶6, and their formation was followed spectrophotometrically. Compounds isolated were identified by elementary analysis and characterized by thermogravimetric analysis and IR-absorption spectroscopy. Coordination sites of o-hydroxybenzohdrazide are discussed with reference to the characteristic IR-absorption bands of the-CONHNH₂ and phenolic groups.     

Darstellung,Eigenschaften und elektronische Raman-Spektren von Bis(chloro)phthalocyaninatoferrat(III), -ruthenat(III) und -osmat(III)

Preparation, Properties and Electronic Raman Spectra of Bis(chloro)-phthalocyaninatoferrate(III), -ruthenate(III) and -osmate(III) Bis(chloro)phthalocyaninatometalates of Fe^III, Ru^III and Os^III [MCl₂Pc(2-)]^?, with an electronic low spin ground state are formed by the reaction of [FeClPc(2-)] resp. H[MX₂Pc(2?)] (M = Ru, Os; X = Cl, I) with excess chloride in weakly coordinating solvents (DMF, THF) and are isolated as (n-Bu₄N) salts. The asym. M? Cl stretch (ν_as(MCl)) is observed in the f.i.r. at 288 cm^?1 (Fe), 295 cm^?1 (Ru), 298 cm^?1 (Os), ν_as(MN) at 330 cm^?1 (Fe), 327 cm^?1 (Ru), and 317 cm^?1 (Os); only ν_s(OsCl) at 311 cm^?1 is resonance Raman (r.r.) enhanced with blue excitation. The m.i.r. and FT-Raman spectra are typical for hexacoordinated phthalocyanines of tervalent metal ions. The UV-vis spectra show besides the characteristic π-π* transitions (B, Q, N, L band) of the Pc ligand a number of extra bands at 12–15 kK and 18–24 kK due to trip-doublet and (Pc→M)CT transitions. The effect of metal substitution is discussed. The r.r. spectra obtained by excitation between the B and Q band (λ₀ = 476.5 nm) are dominated by the intraconfigurational transition Γ₇ Γ ₈ arrising from the spin-orbit splitting of the electronic ground state for Fe^III at 536 cm^?1, for Ru^III at 961 cm^?1 and Os^III at 3 028 cm^?1. Thus the spin-orbit coupling constant increases very greatly down the iron group: Fe^III (357 cm^?1)< Ru^III (641 cm^?1)< Os^III (2 019 cm^?1). The Γ₇ Γ ₈-transition is followed by a very pronounced vibrational finestructure being composed in the r.r. spectra by the coupling with ν_s(MCl), δ(MClN) and the most intense fundamental vibrations of the Pc ligand. In absorption only vibronically induced transitions are observed for the Ru and Os complex at 1 700-2800 rsp. 3100-5800 em^?1 instead of the 0-0 phonon transitions. The most intense lines are attributed to combinations of the intense odd vibrational mo-des at ≈ 740 and 1120 cm^?1 with ν₅(MCI), δ(MClN).     

Chlorokomplexe von Ti(III), V(III) und Cr(III) in Propandiol-1,2-carbonat und Trimethylphosphat

Addition of chloride ions to the hexasolvated ions of Ti(III), V(III) and Cr(III) in propandiol-1,2-carbonate (PDC) and trimethylphosphate (TMP) may lead to the following complexes: [TiCl]²⁺ (inPDC), [TiCl₂]⁺ (inTMP), TiCl₃ (inPDC andTMP, low solubility inTMP), [TiCl₄]^? (inPDC andTMP?), [TiCl₆]^3? (inPDC); [VCl]²⁺ (inPDC andTMP), VCl₃ (inPDC andTMP, low solubility inTMP), [VCl₄]^? (inPDC); [CrCl]²⁺ (inTMP), [CrCl₂]⁺ (inPDC), CrCl₃ (inPDC andTMP), [CrCl₄]^? (inPDC).     

Eisen (III) und Aluminium

Ohne Zusammenfassung     

Darstellung und Untersuchung neuer komplexer Jodverbindungen von Indium(III) und Gallium(III)

The present work contains the preparation, for the first time, of complex iodo acids of gallium(III) and indium(III) as well as the preparation of compounds of these acids with pyridine and aniline. A study of some of the chemical and physical properties of these acids and the UV and IR spectra of the pyridine and aniline compounds are also described.     

cis- und trans-Disulfitotetracyanokobaltate(III)

The preparation and the properties of a series of salts containing the new anion cis-[Co(SO₃)₂(CN)₄]^5? are described. The method of preparation of the trans[Co(SO₃)₂ · (CN)₄^5? complex is improved and the new salt K₄[CoSO₃(CN)₅] · 4H₂O is described. The configuration of the cis- and trans-[Co(SO₃)₂(CN)₄]^5? complexes results from their Raman, IR and UV spectra.     

Ultramikromengen der Trifluoracetylacetonate von Chrom (III), Aluminium-(III) und Rhodium(III)

Ohne Zusammenfassung     

Gemeinsame polarographische Bestimmung von Arsen(III) und Antimon(III)

Zusammenfassung Die in schwach alkalischen Grundlösungen auftretende, sehr gut ausgebildete Arsenwelle ist bei Anwesenheit von Antimon, das vorher abgeschieden wird, nicht mehr auswertbar. Dagegen kann im schwach sauren Bereich für die gemeinsame Sb-As-Bestimmung eine Mischung aus 2 Teilen gesättigter Calciumhydroxidlösung und 8 Teilen 0,1 m Citronensäure als Grundlösung (p_H 2,5) verwendet werden. Darin lassen sich Antimon und Arsen bei vergleichbaren Mengenverhältnissen gut nebeneinander aus einem Polarogramm bestimmen. Nachweisbar ist Arsen neben Antimon bis zu einem Molverhältnis SbAs wie 601. Die Antimonstufe wird nur durch Blei und Cadmium, die Arsenstufe durch Nickel und Zink gestört.     

Synthese und Eigenschaften von Intramolekular stabilisierten Gallium(III)- und Indium(III)-Verbindungen

Synthesis and Properties of Intramolecular Stabilized Gallium(III) and Indium(III) Compounds Novel organogallium and organoindium compounds containing stabilizing diphenylalkylphosphane, -stibane and -bismutane ligands are synthesized. The intramolecular coordination by formation of a metal(13)-metal(15) bond is proved by ¹H-NMR studies.     

Darstellung und Charakterisierung von bindungsisomeren Hexakis(thiocyanato-isothiocyanato)-iridaten(III) und einiger Chloro-, Cyano-pentarhodanoiridate(III)

Preparation and Characterization of Bond-Isomeric Hexakis(thiocyanato-isothiocyanato)-iridates(III) and Some Chloro-, Cyano-pentarhodanoiridates(III) The evaporated ethanolic extract of the reaction product of K₃[IrCl₆] and HNO₃, refluxed with an aqueous KSCN solution yields a mixture of the bond isomers [Ir(NCS)_n(SCN)_6?n]^3?, n = 0–2 and small amounts of bond isomeric chloropentrahodanoiridates(III). By heating the tetrabutylammonium salts, N coordination of the ambident SCN^? is favoured forming compounds with n = 2–5 beside chloro- and cyanopentarhodanoiridates(III). With n = 2, 3 pairs of geometric isomers can be detected. The pure compounds are separated by ion exchange chromatography on diethylaminoethylcellulose. The trans/mer-complexes migrate 1.9 times faster than the cis/fac-isomers. Depending on S- or N-bonding the IR and Raman spectra show typical vibrations: ν_CN(N) and ν_CN(S): 2100–2175, ν_CS(N): 810–855, ν_CS(S): 690–710, δ_NCS: 470–480, δ_SCN: 420–470, ν_IrN: 300–325, ν_IrS: 255–313 cm^?1. Except the inner ligand vibrations the Rh? N and Rh? S valence frequencies are assigned according to the supposed point symmetries. By interaction of the trans-positioned ligands characteristic shifts are caused.     

Monomere und dimere Chrom(III)-Phthalocyanine: Synthese und Eigenschaften von Hydroxopyridinophthalocyaninatochrom(III) und μ-Oxodi(pyridinophthalocyaninatochrom(III))

Monomeric and Dimeric Chromium(III) Phthalocyanines: Synthesis and Properties of Hydroxopyridinophthalocyaninatochromium(III) and μ-Oxodi(pyridinophthalocyaninatochromium(III)) Heating of ?[Cr(OH)Pc^2?]”? in pyridine (Py) gives the paramagnetic (T = 273 K) complexes [Cr(OH)(Py)Pc^2?] (μ_Cr = 3.84 μ_B) and [(Cr(Py)Pc^2?)₂O] (μ_Cr = 1.24 μ_B) by consecutive substitution and condensation reactions. The UV-VIS spectra are characterized by the typical B, Q, and N regions of the Pc^2? ligand being shifted hypsochromically for the dimer with respect to the monomer due to excitonic coupling (1.5 kK). Regions of weak absorbance between 8 and 13 resp. 19 kK are assigned to trip-quartet transitions for both complexes. A weak band at 870 cm^?1 in the FIR/MIR spectra is assigned to v_as(Cr? O? Cr). In the resonance Raman(RR) spectra v(Cr? O) at 514 cm^?1 resp. v_s(Cr? O? Cr) at 426 cm^?1 is selectively enhanced. Further strong RR-lines of the μ-Oxo dimer at 110 and 631 cm^?1 are assigned to a (Py? Cr? O)- resp. internal pyridine deformation of a_1g symmetry. An assignment as 2v_as(Cr? O? Cr) is proposed for the remarkable RR line at 1740 cm^?1.     

Kinetik und Mechanismus des Ligandentausches zwischen Thallium(III)oxinat und Eisen(III) in Propylencarbonat

The transfer of oxinate ions from thallium (III)oxinate to trivalent Fe(DMF) ₆ ³⁺ in propylenecarbonate takes place via rearrangements within a rapidly formed binuclear thallium(III)—iron(III) complex. In a last rapid step this rearranged complex reacts with excess reactants to the final products whose composition accordingly depends on the ratio of the reactant concentrations.

     

Über die Synthese von Hydrazinium-hexafluorovanadat(III) und Hydrazinium-hexafluorochromat(III)

Ohne Zusammenfassung     

Sulfonazo (I) und sein Dibrom (II)- und Dimethylderivat (III)

Ohne Zusammenfassung     

Hexamminmetall(III)-hexachlorochromate(III): Darstellung,Kristallgitter und Spektren

Hexammine-metal(III) hexachlorochromates(III). Preparation, crystal lattic and spectra The preparation of [Me(NH₃)₆]CrCl₆ with Me = Co and Rh from aqueous solutions and with Me = Co, Cr and Rh by thermal dehydratation is given. The crystal structure of these compounds is T_h⁶? Pa3, Z = 4. The absorption spectrum shows the two known spin allowed bands at 13300 and 1890C cm^?1. Some weak vibronic absorptions are observed from 13870 cm^?1 to 15130 cm^?1. The vibrational spectrum of CrCl₆^2? has been completed by the measurement of the RAMAN spectrum, the IR spectra have been reinvestigated. The vibrational spectra confirm the nearly undisturbed octahedral symmetry of the hexahalogenometallate anion which has previously been observed for similar compounds.