Zur Kenntnis der Sulfito-kobalt(III)-Ammine. I. Sulfitopentammin- und Sulfitoaquotetramminkobalt(III)-Salze

Sulphito Cobalt (III) Ammines. I. Sulphitopentaamminecobalt (III) and Sulphitoaquotetraamminecobalt(III) Salts Because of the trans effect of the sulphito group salts containing the cation [CoSO₃(NH₃)₅]⁺ react with H₂O forming [CoSO₃H₂O(NH₃)₄]⁺. In acid medium the conversion is complete. Therefore, sulphitopentaamminecobalt(III) salts have to be prepared and purified in solutions containing free ammonia. Earlier preparation methods not regarding this circumstance lead to tetraammine compounds or to mixture of pentaammine and tetraammine complexes. The preparation and the properties of a number of sulphitopentaammine and sulphito-aquotetraamminecobalt(III) salts are described (see “Inhaltsübersicht”). The light absorption and the IR spectra of the complexes [CoSO₃(NH₃)₅]⁺ and [CoSO₃H₂O(NH₃)₄]⁺ are reported and discussed.     

Zur Kenntnis der Sulfito-kobalt(III)-Ammine. II. [CoSO3NCS(NH3)4] und [CoSO3SCN(NH3)4]

Sulphito Cobalt(III) Ammines. II. [CoSO₃NCS(NH₃)₄] and [CoSO₃SCN(NH₃)₄] The brown complex [CoSO₃NCS(NH₃)₄] · 2 H₂O formed from aqueous solutions contains N-bonded thiocyanate as concluded from his IR spectrum. After dehydration the red complex [CoSO₃SCN(NH₃)₄] containing S-bonded thiocyanate has been formed. The conversion of the two isomers is favoured by the trans effect of the sulphito group.     

Zur Kenntnis der Ammonium-fluoromanganate(III)

Investigation of the system MnF₃–NH₄F–HF–H₂O revealed considerable hydrolysis even in highly acidic media. NH₄MnF₄ with a tetragonal unit cell,a=7.752 (6),c=6.153 (12) Å andZ=4, was isolated together with the already known (NH₄)₂MnF₅ and (NH₄)₃MnF₆. No splittings of the valence modes were observed with hexa- and penta-fluoromanganates, although the deformation of the octahedra was evident. Splitting was characteristic of the tetrafluoro compound. The spectrum of ammonium ion indicated increasing hydrogenbonding in the sequence hexa-, penta-, tetra-fluoromanganate.

---

---

9. Mitt.: Mh. Chem.106, 1333 (1975).     

Zur Kenntnis der Hexafluorocuprate(III)

On Hexafluorocuprates (III) New prepared are: Cs₂LiCuF₆ (green, trigonal isotypic to Cs₂LiGaF₆; a = 621.5, c = 503.3 pm, γ = 120° from CsCuCl₃, CsCl, Li₂CO₃, p_F2 = 1 bar, 350°C, 2w); K₂LiCuF₆ (green, cubic isotypic to K₂NaCrF₆; a = 792.5 pm from KCuCl₃, Li₂CO₃, KCl, p_F2, = 35 bar, 480°C, 3 d); CsRb₂CuF₆ (green, cubic isotypic to inv. K₂NaCrF₆; a =899,6 pm from CsCuCl₃, RbCl, p_F2 = 1 bar, 400°C, 7 d); CsRbKCuF₆ (green, cubic isotypic to K₂NaCuF₆; a = 886.1 pm from KCuCl₃, CsCl, RbCl, p_F2 = 1 bar, 400°C, 7 d); CsCuCuF₆ (black, orthorhombic isotypic to CsNiNiF₆; a = 706.7, b = 727.7, c = 1032.2 pm from CsCuCl₃, CuCl₂ · 2H₂O, p_F2 = 30 bar, 400°C, 20 h); CsBaCuF₆ (green, tetragonal; a = 598.1, c = 864.6 pm from ?BaCuO₂’?, CsCl, p_F2 = 350 bar, 400°C, 7 d). Also prepared: Cs₂RbCuF₆, Cs₂KCuF₆, Cs₂NaCuF₆, Rb₂KCuF₆, Rb₂NaCuF₆, Rb₂LiCuF₆, K₂NaCuF₆, Na₃CuF₆, K₃CuF₆, Rb₃CuF₆, Cs₃CuF₆ and CsZnCuF₆ (parameters see text). The Madelungpart of Lattice Energy, MAPLE are calculated and discussed. All samples are paramagnetic and follow (exception: CsZnCuF₆) the Curie-Weiss-Law.     

Zur Kenntnis der Hexafluoromanganate(III)

The preparation of the up to now unknown compounds [Co(NH₃)₆]MnF₆, [Cr(NH₃)₆]MnF₆ and [Rh(NH₃)₆]MnF₆ is reported. The compounds crystallize in the space group T_h⁶–Pa3, with four formula units in a cell. The magnetic moment of [Co(NH₃)₆]MnF₆ has been measured (4,94 B.M.). The spectra of the above compounds and of K₃MnF₆ and K₂NaMnF₆ in the ultraviolet, visible and infrared region have been measured and discussed. The static distortion of MnF^3?₆ in K₃MnF₆ and K₂NaMnF₆ and a dynamic effect of the compounds with a complex cation due to the JAHN -TELLER theorem show two different types of infrared spectra.     

Zur Kenntnis der Mono-ethylendiamin-cobalt(III)-Komplexe

Preparation and Properties of Mono-ethylenediaminecobalt (III) Complexes [Co(N₃)₃en]₂ and [CoCl₂(H₂O)₂en]Cl are useful starting materials for the preparation of numerous mixed-ligand complexes of Co^III containing one molecule of ethylenediamine. The preparation and the properties of a series of new compounds are described. Improved methods for the preparation of known complexes are given (see Inhaltsübersicht).     

Zur Kenntnis der Kjeldahl-Reaktion III

Zusammenfassung Chromatographische Versuche zeigen, daß die Zwischenprodukte der Kjeldahlisierung des Anilins mit denen der Anilinschwarz-Bildung verwandt sind. Die Elementaranalyse von Polymerisationsprodukten dieser Zwischenstoffe weist darauf hin, daß es sich um sulfonierte Oxyemeraldine handelt. Kinetische Versuche und Überlegungen führen zu dem Ergebnis, daß alle diese Zwischenstufen erst durchlaufen werden, nachdem Anilin zu Sulfanilsäure sulfoniert worden ist, wobei ein der weiteren Oxydation vorgelagertes Gleichgewicht erreicht wird. Emil Abel zum 80. Geburtstag zugeeignet.     

Zur Kenntnis der Amyrine III

Ohne Zusammenfassung     

Zur Kenntnis der Netzhautstoffe III

Ohne Zusammenfassung1. Mitteilung:Brunner, Baroni undKleinau, Hoppe-Seylers Z. physiol. Chem.236 (1935) 257; 2. Mitteilung:Brunner u.Kleinau, Mh. f. Chem.68 (1936) 244, bzw. S.-B. Akad. Wiss. Wien IIb 5 (1936) 464.Die vorliegende Arbeit wurde seitens der Akademie der Wissenschaften in Wien durch eine Subvention aus den Mitteln der Zachstiftung gefördert. Wir gestatten uns auch an dieser Stelle unseren Dank hiefür auszusprechen.     

Zur Kenntnis der Adsorption,III

Ohne Zusammenfassung     

Zur Kenntnis von Natrium-hexafluoromanganat(III)

Sodium hexafluoromanganate(III) has been synthesized by heating equimolecular quantities of Na₂MnF₅ and NaF in argon atmosphere. The compound is monoclinic witha=5.56 (1) Å,b=5.84 (1) Å,c=8.10 (2) Å, =90.7 (2) andZ=2. It is a high spin complex with _eff and the deformation of the octahedra is evident from its IR-spectra. Two enantiotropic transitions (at 562 and 653°C) and the melting point at 800°C have been observed.

---

---

8. Mitt.: Mh. Chem.106, 483 (1975).     

Zur Kenntnis des Natriumthioferrates(III)

The mixed valency compound Na₃Fe₂S₄, which is also formed in iron-sodium polysulfide melts, is oxidized and hydrated to NaFeS₂·H₂O (x ≈ 2) on air. It is shown by TGA that this hydrate loses the water reversibly between 80–140 °C. A crystal structure model for the water free phase NaFeS₂ is proposed (space group I 222,a=6.25 Å,b=10.83 Å,c=5.40 Å). The formation of NaFeS₂·xH₂O from Na₃Fe₂S₄ and the reversible phase transformation between NaFeS₂·xH₂O and NaFeS₂ are topotactic. Na⁺ ions in NaFeS₂·xH₂O are easily exchanged against K⁺, Rb⁺, Cs⁺, Tl⁺, Ca²⁺, Sr²⁺, and Ba²⁺. The high chemical reactivity of the sodium thioferrates is discussed and their crystal structures are compared with the other alkali metal thioferrate structures.     

Zur Kenntnis der Bis(dialkylamino)acyloxiborane

About Bis(dialkylamino)acyloxyboranes By reactions of bis(dialkylamino)bromoborane with potassium, lead, silver or trialkylammonium salts of corresponding carboxylic acids the above listed compounds have been prepared. Some properties of the compounds are described.