Bromo- und Rhodanokomplexe des Vanadyl(IV)ions in Acetonitril, 1,2-Propandiol-carbonat,Trimethylphosphat und Dimethylsulfoxid

The formation of bromo- and thiocyanatocomplexes of VO²⁺(IV) has been investigated in acetonitrile (AN), trimethylphosphate (TMP), 1,2-propanediol-carbonate (PDC) and dimethylsulfoxide (DMSO) by spectrophotometric, potentiometric and conductometric methods. The following coordination forms are indicated to be present in solution: [VOBr]⁺ (inAN andPDC), [VOBr₂] (inAN andPDC), [VOBr₃]^? (inPDC?), [VOBr₄]^2? (inAN andPDC), [VO(NCS)]⁺ (inAN, PDC andDMSO), [VO(NCS)₂] (inAN, PDC andTMP), [VO(NCS)₃]^? (inAN, PDC andTMP), [VO(NCS)₄]^2? (inAN, PDC, TMP andDMSO). The results are discussed using the donor numbers of the respective solvents.     

Bromokomplexe von Co(II) und Ni(II) in Acetonitril,Propandiol-1,2-carbonat und Trimethylphosphat

Zusammenfassung Die Bildung von Bromokomplexen von Co(II) und Ni(II) wird in Acetonitril (AN), Propandiol-1,2-carbonat (PDC) und Trimethylphosphat (TMP) auf spektrophotometrischem, potentiometrischem und konduktometrischem Wege untersucht. Folgende Koordinationsformen dürften vorliegen: [CoBr]⁺ (oktaedrisch inAN undTMP), CoBr₂ (tetraedrisch inAN, oktaedrisch inTMP), [CoBr₃]^– (tetraedrisch inAN, oktaedrisch inTMP), [CoBr₄]^2– (tetraedrisch inAN undPDC, oktaedrisch inTMP), [NiBr]⁺ (oktaedrisch inAN), NiBr₂ (tetraedrisch inAN, oktaedrisch inTMP), [NiBr₃]^– (tetraedrisch inAN), [NiBr₄]^2– (tetraedrisch inAN undPDC, oktaedrisch inTMP).

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The formation of bromo complexes of Co(II) and Ni(II) is investigated in acetonitrile (AN), propanediol-1,2-carbonate (PDC) and trimethylphosphate (TMP) by spectrophotometric, potentiometric and conductometric methods. The following coordination forms are reported: [CoBr]⁺ (octahedral inAN andTMP), CoBr₂ (tetrahedral inAN, octahedral inTMP), [CoBr₃]^– tetrahedral inAN, octahedral inTMP), [CoBr₄]^2– (tetrahedral inAN andPDC, octahedral inTMP), [NiBr]⁺ (octahedral inAN), NiBr₂ (tetrahedral inAN, octahedral inTMP), [NiBr₃]^– (tetrahedral inAN), [NiBr₄]^2– (tetrahedral inAN andPDC, octahedral inTMP).

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Bromokomplexe von Mn(II) und V(III) in Acetonitril,Propandiol-1,2-carbonat und Trimethylphosphat

Zusammenfassung Die Bromokomplexe von Mn(II) und V(III) inAN, PDC undTMP wurden auf spektrophotometrischem, potentiometrischem und konduktometrischem Wege untersucht. Folgende Koordinationsformen dürften vorliegen: [MnBr]⁺ (inAN), MnBr₂ (tetraedrisch inAN), [MnBr₃]^– (tetraedrisch inAN), [MnBr₄]^2– (tetraedrisch inAN undPDC); [VBr]²⁺ (oktaedrisch inTMP), [VBr₂]⁺ (oktaedrisch inAN), VBr₃ (oktaedrisch inAN), [VBr₄]^– (oktaedrisch inAN undPDC).

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Bromocomplexes of Mn(II) and V(III) were investigated inAN, PDC andTMP by spectrophotometric, potentiometric and conductometric methods. The presence of the following species is indicated: [MnBr]⁺ (inAN), MnBr₂ (tetrahedral inAN), MnBr₃]^– (tetrahedral inAN), [MnBr₄]^2– (tetrahedral inAN) andPDC); [VBr]²⁺ (octahedral inTMP), [VBr₂]⁺ (octahedral inAN), VBr₃ (octahedral inAN), [VBr₄]^– (octahedral inAN andPDC).

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Bromo-, Chloro-, Rhodano- und Azidokomplexe des Vanadyl(IV)ions in Nitromethan

Zusammenfassung Die Bildung von Bromo-, Chloro-, Rhodano- und Azidokomplexen von VO²⁺ wurde in Nitromethan auf spektrophotometrischem, potentiometrischem und konduktometrischem Wege untersucht. Die Regel, daß ein Lösungsmittel geringer Donorzahl auch die Bildung schwacher Komplexe gestattet, wird bestätigt.

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The formation of bromo-, chloro-, thiocyanato- and azidocomplexes of VO²⁺ has been investigated in nitromethane by spectrophotometric, potentiometric and conductometric methods. The rule is confirmed that solvents of low donor number will allow also the formation of weak complexes.

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Azidokomplexe in nichtwäßrigen Lösungsmitteln, 3. Mitt.: Ti(III), V(III) und Cr(III) in Acetonitril,Propandiol-1,2-carbonat und Trimethylphosphat

Ions of Ti(III), V(III) and Cr(III) seem to be converted to the following azido complexes in acetonitrile, propanediol-1,2-carbonate and trimethylphosphate: [Ti(N₃)₂]⁺ (inTMP), Ti(N₃)₃ (probably distorted octahedral inAN, PDC andTMP, low solubility inTMP), [Ti(N₃)₄]^? (probably tetragonal inAN, probably octahedral inTMP), [Ti(N₃)₆ ^3? (probably distorted octahedral inAN andPDC); [V(N₃)]²⁺ (inAN, PDC andTMP), V(N₃)₃ (octahedral inAN, PDC andTMP, low solubility inTMP), [V(N₃)₄]^? (inPDC), [V(N₃)₆]^3? (octahedral inAN andPDC); [Cr(N₃)]²⁺ (inTMP), [Cr(N₃)₂]⁺ (octahedral inAN andPDC), Cr(N₃)₃ (octahedral inAN, PDC andTMP), [Cr(N₃)₆]^3? (octahedral inAN andPDC).     

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).     

Koordinationsformen des Eisen(III)-chlorids in Trimethylphosphat und Dimethylsulfoxid

Zusammenfassung Die Koordinationsform des Eisen(III)-chlorids in Trimethylphosphat und Dimethylsulfoxid wurden konduktometrisch, spektrophotometrisch und potentiometrisch untersucht. Mit Sicherheit wurden in Trimethylphosphat Fe _sv ³⁺ , [FeCl₃]_sv und [FeCl₄]^– und in Dimethylsulfoxid Fe _sv ³⁺ identifiziert.Mit 5 Abbildungen     

Azidokomplexe in nicht-wäßrigen Lösungen, 1. Mitt.: Co(II), Ni(II) und Cu(II) in Acetonitril,Trimethylphosphat und Dimethylsulfoxid

The formation of azido complexes is investigated inDMSO, TMP andAN by spectrophotometric, potentiometric (Tl/TlN₃-electrode) and conductometric methods. The following coordination forms were established: [CoN₃]⁺ (octahedral, inTMP), [Co(N₃)₂] (tetrahedral, inTMP, AN andDMSO), [Co(N₃)₄]^2? (tetrahedral, inTMP, AN andDMSO); Ni(N₃)₂ and [Ni(N₃)₄]^2? (either, inTMP, AN andDMSO), [CuN₃]⁺ and [Cu(N₃)₂] (both inTMP, AN andDMSO), [Cu(N₃)₃]^? (tetrahedral, inTMP andAN) and [Cu(N₃)₄]^2? (tetrahedral, inTMP, AN andDMSO).     

Leitfähigkeitsuntersuchungen in Hexamethylphosphorsäuretriamid und Propandiol-1,2-carbonat

Limiting conductances, dissociation constants and ion conductances have been determined for a number of tetrabutylammonium and lithium salts in the solvents hexamethylphosphoric triamide (HMPT) and propanediol-1.2-carbonate (PDC). LiCl and LiBr are completely dissociated inHMPT, but are associated inPDC. The reverse behaviour is found for the corresponding tetrabutylammonium salts. Conductance measurements show thatHMPT is a strongly differentiating solvent for the donor strength of halide and perchlorate ions.     

Azido-, Rhodano-, Cyano- und Fluorokomplexe des Fe(III)-Ions in Dimethylsulfoxid

Zusammenfassung Auf Grund spektrophotometrischer und konduktometrischer Messungen wurden folgende Koordinationsformen des Eisen(III)-ions mit Azid-, Rhodanid-, Cyanid- und Fluoridionen in Dimethylsulfoxid festgestellt: [Fe(N₃)₄]^–, [Fe(SCN)₆]^3–, [Fe(CN)₂]⁺, Fe(CN)₃, [Fe(CN)₄]^–, [FeF₂]⁺, [FeF₄]^–.

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By means of spectrophotometric and conductometric measurements the following coordination forms of iron(III) with azide-, thiocyanate-, cyanide- and fluoride ions were found in dimethyl sulfoxide: [Fe(N₃)₄]^–, [Fe(SCN)₆]^3–, [Fe(CN)₂]⁺, Fe(CN)₃, [Fe(CN)₄]^–, [FeF₂]⁺, [FeF₄]^–.

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Darstellung und Eigenschaften von Vanadyl(IV)-Saccharinat

Summary The synthesis of a new vanadyl(IV)/saccharin complex is reported. Its bonding characteristics differ considerably from all known divalent metal-saccharinates. In this complex a VO(OH)⁺ moiety is coordinated to a saccharin molecule through its carbonyl oxygen and to a saccharinate ion through its deprotonated nitrogen. Two water molecules complete the coordination sphere. X-ray powder diagrams, infrared- and electronic absorption-spectra were recorded and analyzed for the characterization of the compound and its coordination properties. Besides, the magnetic susceptibility and the thermal behaviour were also investigated.

     

Spektrophotometrische Untersuchungen an Komplexen des Zirkonium (IV)-Ions mit Polyoxyflavonen

Zusammenfassung Die Farbreaktion von Zirkoniumperchlorat mit Flavonol und Myricetin wurde nach der spektrophotometrischen Methode von P. Job untersucht. In 2 m-Perchlors?ure bilden beide Flavonole Chelate der st?chiometrischen Zusammensetzung 1∶1 und 1∶2. Angen?herte Werte für die Dissoziationskonstanten der 1. Stufe und die relativen Dissoziationskonstanten der 2. Stufe werden angegeben. Die Konstanten beider Verbindungen zeigen innerhalb der Fehlerbreite übereinstimmung. Daraus wird geschlossen, da\ auch im Myricetin die bevorzugte Stelle der Komplexbildung die ortho-Enolgruppe des Moleküls ist. I. Mitteilung, L. H?rhammer u. R. H?nsel ⁵, siehe auch L. H?rhammer, R. H?nsel u. W. Hieber ⁷.     

Alkalisalze eines neuen Vanadat(IV,V)-Ions

Zusammenfassung Durch homogene Acidifizierung von NH₄-, Na- bzw. K-Thiovanadatlösungen wurden die Salze (NH₄)₂V₃O₈·1/2 H₂O, Na₃V₅O₁₂·8 H₂O und K₃V₅O₁₂·5 H₂O kristallin hergestellt. Die beiden letzteren lassen sich als Dekavanadate(IV, V) mit dem Anion [V₈ ^IVV₂ ^VO₂₄]^6– formulieren und bilden so weitere Glieder einer schon bekannten Reihe entsprechender Anionen mit dem V^IVV^V-Verhältnis 28 bis 73.

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Homogeneous acidification of solutions of NH₄-, Na-, or K-thiovanadates yield the crystalline salts (NH₄)₂V₃O₈·1/2 H₂O, Na₃V₅O₁₂·8 H₂O and K₃V₅O₁₂·5 H₂O. The latter two can be formulated as decavanadates(IV,V), containing the anion [V₈ ^IVV₂ ^VO₂₄]^6– and constituting new members of a series of already known anions with ratios of V^IVV^V from 28 to 73.

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6. Mitt.:E. Hayek undU. Pallasser, Mh. Chem.99, 2126 (1968).     

High- und Low-Spin-Verhalten des Ni3+ -Ions in oktaedrischer Koordination. (A) NiF-Polyeder

High and Low Spin Behaviour of Ni³⁺?Ions in Octahedral Coordination The compounds Cs₂NaNiF₆, Cs₂KNiF₆, Rb₂KNiF₆, K₃NiF₆, and Na₃NiF₆ were investigated by ligand field and EPR spectroscopy between 298 and 4,2 K. These fluorides ? with the exception of the first one – crystallise in the cubic elpasolite lattice or in distorted modifications of this structure type and contain the Ni³⁺ ions in the low spin configuration te. This configuration is stabilised versus the high spin alternative te by an appreciable Jahn-Teller splitting of the ²E_g-state of about 7000 cm^?1. The NiF₆-octahedra are tetragonally elongated, the distortion being dynamical at 298 K. In case of the cubic compound Rb₂KNiF₆ a transition to a tetragonal structure with c/a > 1 as a consequence of a ferrodistortive Jahn-Teller ordering is observed at lower temperatures. It is calculated from the anisotropic g-parameters, that the first excited quartet level ⁴A_2g(⁴T_1g ? te) has an energy which is about 1000 cm^?1 higher than that of the ²A_1g(²E_g ? te) groundstate. Spin-orbit interactions between the energetically neighboured ²A_1g(²E_g) and ⁴A_2g, ⁴E_g(⁴T_1g) states lead to third order contributions to the g-factors, which are very sensitive with respect to the doublet-quartet separation. In the hexagonal compound Cs₂NaNiF₆ finally, in which half of the Ni³⁺ ions occupy octahedral sites connected by common corners as in the other fluorides, while the other half is located in octahedral sites with common faces, high and low spin Ni³⁺ ions are found side by side. Obviously the latter half of these Ni³⁺ ions is geometrically restricted with respect to a Jahn-Teller distortion and hence the high spin configuration energetically favoured.     

Die spektralphotometrische Bestimmung des Kupfer (II)-Ions

Ohne Zusammenfassung     

Das Redoxverhalten des Hexakismethylisonitrilmangan(I)-Ions in Propylencarbonat

Employing voltammetric and polarographic methods the hexakismethylisonitrilemanganese(I) [Mn(L)₆ ⁺] ion was found to undergo two oxidation steps to hexakismethylisonitrilemanganese(II) and hexakismethylisonitrilemanganese(III) as well as a reduction to the metal. Using bisbiphenylchromium(I) iodide [BBCr(I)I] throughout this study as a reference system cyclic voltammetry yielded a value of 2.29 V for the oxydation Mn(L)₆ ²⁺/Mn(L)₆ ³⁺ and 1.11 V for the oxydation Mn(L)₆ ⁺/Mn(L)₆ ²⁺ vs.BBCr(I)I. The half wave potential on the dropping mercury electrode for the oxidation Mn(L)₆ ⁺/Mn(L)₆ ²⁺ aggreed within the limits of experimental error with the value obtained by cyclic voltammetry, theE _1/2 for the reduction was found to be –1.87 V vs.BBCr(I)I. Large scale electrolysis, coulometry and the rotating platinum electrode were used to learn about the nature of the reaction and the reaction products. 0.1M solutions of tetraethylammonium perchlorate tetrabutylammonium perchlorate and tetraethylammonium nitrate served as supporting electrolytes. The standard rate constant for the reaction Mn(L)₆ ⁺/Mn(L)²⁺ was 1.1·10^–2 cm·sec^–1 and for the reaction Mn(L)₆ ²⁺/Mn(L)₆ ³⁺ 4,7·10^–3 cm·sec^–1. The UV-spectra of Mn(L)₆ ⁺ and Mn(L)₆ ²⁺ were also recorded.     

Synthese,Eigenschaften und Kristallstruktur des cis-Dichloro-bis(diethyldithiophosphinato)titan(IV)

Synthesis, Properties, and Crystal Structure of cis-Dichloro-bis(diethyldithiophosphinato)-titanium(IV) By reaction of TiCl₄ with dialkyldithiophosphinic acids R₂P(S)SH (R ? CH₃, C₂H₅) red chelates (R₂PS₂)₂TiCl₂ are obtained which are very sensitive to hydrolysis. Crystal structure analysis of the ethyl compound shows a distorted octahedral chromophor TiS₄Cl₂ with cis-configuration.     

Relative polarographische Halbstufenpotentialreihen in Dimethylsulfoxid (DMSO) und Dimethylformamid (DMF)

Ohne Zusammenfassung