Über Eisen(III)-Komplexe mit Phenolen. V. Komplexbildung mit 4,5-Dibrombrenzcatechin-disulfonsäure(3,6)

The chelate formation between Fe³⁺ and 4.5-dibromopyrocatechol-3.6-disulfonic acid in aqueous solution has been investigated spectrophotometrically. The stability constants and the light absorption properties of the chelates are communicated. Compared with the bromine-free tiron, the ? values increase and the λ_max positions are shifted bathochromically on halogenation. However, due to the changed position of the sulfo groups, the bond-weakening effect of the halogen substituents is covered, leading to a distinct increase of pK_S1, but to only slight alterations of all the other constants. Poor solubility and accessability of the chelating reagent hinder its application in analysis.     

Über Ternäre Chelate des Eisen(III)-Ions mit Nitrilotriessigsäure und Phenolderivaten

On Ternary Chelates of the Iron(III) Ion formed with Nitrilo-Triacetic Acid and Derivatives of Phenol Ternary chelates of iron(III) ions are produced with nitrilo-triacetic acid and some derivatives of phenol in aqueous solution. Their reactions of formation have been controlled by spectro-photometric methods. The ratio of components in the compounds Fe: X: L is 1: 1: 1 without any exception. The measured optical properties (λ_max, ε_max) of the ternary chelates are discussed and compared with the corresponding binary iron(III) phenol chelate.     

Spektrophotometrische Untersuchung der Eisen(III)-Komplexe mit o-Methylbenzamidoxim

The complex formation of Fe³⁺ with o-methyl benzamide oxime was studied spectrophotometrically in methanol solution. The stepwise process gives complexes 1∶1, 1∶2 and 1∶3. The formation constants are lgK ₁ = lg β₁ = 1,88 ± 0,12, lgK ₂ = 3,53 ± 0,2, lgK ₃ = 4,96 ± 0,2, lg β₂ = 1,65 ± 0,32 and lg β₃ = 1,43 ± 0,4, whereK ₃ = β₁ · β₂ · β₃. All measurements were carried out at 25°C and an ionic strength μ=1.     

Über die Reaktion substituierter Thioxanthenoxide mit Säuren

9-[(N-Methyl-3′-piperidyl)-methyl]-thioxanthene-10-oxide (I) on treatment with boiling concentrated hydrochloric acid gives mainly 9-[(N-methyl-3′-piperidyl)-methylene]-thioxanthene (IV) together with small amounts of 9-[(N-methyl-3′-piperidyl)-chloro-methylene]-thioxanthene(II), 9-hydroxy-9-[(N-methyl-3′-piperidyl)-methyl]-thioxanthene (III) and 9-[(N-methyl-3′-piperidyl)-methyl]-thioxanthene (V). Treatment of I with acetic anhydride yields only IV.     

Über das thermische Verhalten einiger Lithium-und Natriumhexafluorometallate(IV)

Thermal Behaviour of Some Lithium and Sodium Hexafluorometallates(IV) Rutile is formed by thermolysis from Li₂TiF₆ and on the other hand at first brookite originates from Na₂TiF₆. The nucleation of the final products is favoured not only by the similarity of the lattice geometries between initial product and final product but also by the chemical influences of small concentrations of defined impurities. The thermal behaviour of the lithium-and sodium haxafluorometalates A₂MF₆ (with M-element of the IV. main group) is compared among one another. The expansion of the lattices and the transformation of the phases are determined with the aid of the high-temperature-Guinier-method and some differences are shown to the same reactions in a great quantity of the substances. It is described γ-Na₂SnF₆ with a Na₂SiF₆ structure type.     

Polyol-Metall-Komplexe. 17. Kristalline Eisen(III)-Komplexe mit zweifach deprotonierten Anhydroerythrit-Liganden

Polyol Metal Complexes. 17. Crystalline Iron(III) Complexes with Twofold Deprotonated Anhydroerythritol Ligands Three new crystalline ferrates(III) with diolato ligands derived from anhydroerythritol by deprotonation have been synthesized from wet alcoholic and from aqueous solution. Almost colourless, monoclinic crystals of Na₂[Fe(AnEryt-H_-2)₂(OH)] · 0.5 NaNO₃ · 3.5 H₂O ( 1 ) have been prepared from ethanolic solutions. They content mononuclear bis diolato hydroxo ferrate(III) dianions. Trinuclear hexakis diolato μ₃-methoxo triferrat(III) tetraanions constitute the anionic part of Na₄[Fe₃(AnErytH_-2)₆(OMe)] · 2.5 NaNO₃ ( 2 ), yellow-green hexagonal crystals of which are formed from wet methanolic solutions. Yellow-green triclinic crystals of Ba₂[Fe₂(AnEryt-H_-2)₄(μ-OH)₂] · 12 H₂O ( 3 ) have been precipitated from aqueous solutions. In 3 , the anions of 1 are dimerized to give tetrakis diolato di-μ-hydroxo diferrat(III) tetraanions.     

Aluminiumalkyle mit Heteroatomen. III. Über Reaktionen von Titan(IV)-chlorid mit Tris(trimethylsilylalkyl)-aluminium-Verbindungen

Aluminium Alkyls with Heteroatoms. III. On Reactions of Titanium(IV) Chloride with Trimethylsilylmethyl Aluminium Compounds Trimethylsilylmethyl titanium trichloride can be obtained by reaction of titanium(IV) chloride with tris(trimethylsilylmethyl)aluminium diethyl ether (1:1). Its catalytic activity for polymerisation of butadiene has been investigated.     

Über die Reaktion von Phenolen mit N-substitutierten Maleinimiden

The Reaction of Phenols with N-substituted Maleinimides Phenoxysuccinimides are formed by the base catalysed addition of phenols to N-substituted maleinimides. In the presence of catalytic amounts of tertiary aliphatic amines yields as high as 90% are obtained. A series of adducts of mono-and di-phenols to mono- and bismaleinimides is described. Pure phenoxysuccinimides are stable compounds but the basic catalysts of their formation give rise to their decomposition into the phenolic component and oligomeric maleinimide. A nucleophilic reaction mechanism both for the formation and the decomposition is discussed. A new crosslinked addition polymer from a diphenol and a bismaleinimide with a surprisingly high heat stability is described.     

Zinn(IV)-Komplexe mit dreizähnigen diaciden Liganden

Tin(IV) Complexes with Tridentate Diacidic Ligands By template reactions including bis(acetylacetonato)-dichloro-tin(IV) and O-aminophenol as well as o-aminothiophenol, benzoylhydrazine, and thiobenzoylhydrazine the tin chelates of tridentate diacidic ligands containing ligator atoms were prepared. To characterize the compound, IR, UV-VIS and Mössbauer spectroscopy were used. Crystal structure analyses demonstrate the existence of disturbed octahedral structures. Bis[acetylacetonbenzoylhydrazonato(2-)]tin(IV): space group P2₁/c, Z = 4, 2501 observed unique reflections, R = 0.045. Lattice dimensions at 20°C: a = 992.3, b = 2405.5, c = 1071.8pm, β = 116.94°. Bis[acetylacetonthiobenzoylhydrazonato(2-)] tin(IV): space group P2₁/c, Z = 4, 3603 observed unique reflections, R= 0.029. Lattice dimensions at 20°C: a = 1581.5, b = 947.8, c = 1644.9pm, β = 90.32°.     

Über Oxidhydroxide des vierwertigen Mangans mit Schichtengitter. 3. Mitteilung. Reduktion von Mangan(III)-manganat(IV) mit Zimtalkohol

Manganese(III) manganate(IV), one of the synthetic varieties of the birnessite group, is readily reduced in xylene suspension by cinnamyl alcohol. At moderate temperatures, including room temperature, γ-MnOOH (manganite) forms topotactically in extremely thin needles and is therefore easily overlooked in the X-ray examination. At higher temperatures further reduction occurs (Mn^III → Mn^II), and Mn₃O₄ (hausmannite) appears in comparatively large, equant cristallites which are less distinctly oriented. For comparison Na₄Mn₁₄O₂₇, 9H₂O, which has also been investigated, is much more stable than Mn₇O₁₃, 5H₂O. The same holds for finely divided synthetic varieties of the birnessite group precipitated from KMnO₄ solutions; by their behaviour they are related to Na₄Mn₁₄O₂₇, 9H₂O rather than to Mn₇O₁₃, 5 H₂O which is consistent with their substantial alkaline ion content. These results raise the question: is the so-called ‘todorokite’ a pure crystal species. According to present data ‘todorokite’ could be regarded as a transition product, i.e. as half decomposed buserite admixed with birnessite and substantial amounts of manganite.     

Über Halogenotitanate(IV)

The preparation of tetraethylammonium slats with following anions is described: [TiBrCl₅]^2?,[TiBr₅Cl]^2?,[TiCl₄Br · CH₃CN]^?, [TiBr₄Cl · CH₃CN]^?, [TiBr₅ · CH₃CN]^? und TiF. The reaction mechanisms is discussed. TiF forms fluorine-bridges giving a polymeric anion. Chlorofluorotitanates(IV) could not be prepared. Mixed halide complexes of Ti(IV), Nb(V) and Ta(V) are compared with analogous complexes of Sn(IV), Pb(IV) and Sb(V).     

Über Oxidhydroxide des vierwertigen Mangans mit Schichtengitter 2. Mitteilung: Mangan (III)-manganat (IV)

The preparation and probable structure of managanese (III)-manganate (IV) Mn₇O₁₃, 5H₂O (a₀ = 2,84, c₀ = 7,27 Å) and manganous (II)-manganate (IV) Mn₇O₁₂, 6H₂O are described. Both consist of platelets. Digesting in diluted HNO₃ leads to γ-MnO₂ (nsutite). Manganese (III)-manganate (IV) is much less stable than the sodiummanganese (II, III)-manganate-(IV) described earlier and looses water easily when heated or in vacuo. Water loss results in breaking down of the double layer lattice, and the product is only two-dimensionally ordered, producing only prism reflections on the X ray diagramm. Heating results in a continuous transition to the two-dimensionally ordered phase, then to a finely divided and very disordered γ-MnO₂, and eventually to a finely divided and disordered β-MnO₂ (pyrolusite). The transition is topotactical so far, but further heating produces δ-Mn₂O₃ without obvious topotactical relations to the earlier products. The so-called ‘δ-MnO₂’ (birnessite) appears to be a family of finely divided and very disordered varieties of such manganates (IV) with part of the Mn³⁺ substituted by Mn⁴⁺. Since such products usually contain remarkable amounts of alkali ions, they are rather varieties of the earlier described sodiummanganese (II, III)-manganate (IV). A provisional explanation of the streaking in the electron diffractions of these manganate (IV). A provisional explanation of the streaking in the electron diffractions of these manganates (IV) is given. With respect to these results the so-called ‘δ-MnO₂’ can no longer be attributed to the true manganese dioxides.     

Reaktion oxygenierter Kobalt (II)-Komplexe. XII. Über einen binuclearen μ-Peroxodikobalt (III)-Komplex mit makrocyclischem Brückenring

Reactions of oxygenated cobalt(II) complexes. XII. A binuclear μ-peroxodicobalt(III) complex with a macrocyclic bridging ring

1 XI: siehe [1].

Singly bridged [(tren) (NH₃) CoO₂(NH₃) (tren)]⁴⁺ reacts with excess tren by replacement of NH₃ in cis-position to the peroxo group and formation of a new type of doubly bridged μ-peroxo complex. An X-ray structure determination of [(tren)-Co(O₂, tren)Co(tren)] (ClO₄)₄ · 2 H₂O showed that the additional tren forms a macrocyclic bridging ring. The conformation of the CoOOCo group is transoid with a dihedral angle of 20°. The crystals are monoclinic with space group P2₁/c. The lattice constants are a = 9,798, b = 26,385, c = 16,385 Å, β = 110,2° with four formula units in the cell. The final R value is 0,124. ClO anions are disordered. The reactions of [(tren)Co(O₂, tren)Co(tren)]⁴⁺ in aqueous solution are compared with those of [(tren) (NH₃) CoO₂Co (NH₃tren)]⁴⁺. In acidic solution the new complex mainly decomposes to Co^II and O₂. In alcaline medium the bridging tren is replaced by an OH bridge, forming the well characterized doubly bridged [(tren)-Co(O₂, OH)Co(tren)]³⁺. Differing from the singly bridged bis (ammino) complex, the reactions of which show no pH dependency at all, the decomposition of the tren bridged complex is H⁺-catalyzed. The kinetic data have been interpreted as (i) preceding fast protonation step which is followed by a conformational change of the bridging ring, (ii) acid hydrolysis of a Co-μ-tren bond and (iii) fast cleavage of the Co-OO bond which is labilized by coordinated H₂O.     

Über die Elektronenspinresonanzspektren einiger Cu2+-Komplexe in wässeriger Lösung

The e.s.r. spectra of aqueous solutions of Cu²⁺-complexes with a series of methylpyridines (PYR) have been investigated at liquid nitrogen temperature. The experimental data indicate that the formula CU(PYR) holds for the compounds in the frozen solutions. The marked decrease of the copper hyperfine coupling constant for some of the complexes is explained in terms of a distortion of the square planar structure towards a tetrahedral environment of the Cu²⁺. An analogous interpretation of the e.s.r. spectra of some copper containing electron-transfer-oxidases, e.g. ceruloplasmin and laccase, presents a possible explanation of the experimentally observed connections between the spectra and the enzymatic activity of these compounds.     

Über die Hydrolyse von Eisen(III)Salzlösungen. I. Die Hydrolyse der Lösungen von Eisen(III)chlorid

When a very diluted iron(III)chloride solution is slowly alkalified by a weak base, the deprotonation of [Fe(H₂O)₆]³⁺ proceeds in a first stage to form mono- and dinuclear hydroxoaquo-complexes. In a second stage 4 dimers condense around a chloride ion to form an eight membered ring, an embryon, which grows fast to very small crystals of the composition Fe₄O₃(OH)₅Cl and the structure of the β-FeOOH. These crystalline micells remain colloidally dissolved. If the pH is raised above approximately 3.4 the Cl^?- are exchanged against OH^?-ions and flocculation occurs. This shows that Pauli, assuming the micells of such sols to be polynuclear complex ions, is basically correct, and it follows that micells can also be micro-crystals. When an iron(III)chloride solution is neutralized fast with a strong base, an ‘amorphous’ precipitation is obtained which gives with MoK_α-X-rays only two broad reflections, showing that the iron oxide hydroxide octahedra are condensed in a highly disordered way. The coherently scattering areas of this precipitate are probably tetramers. Small amounts of primarily formed amorphous iron(III)hydroxide are transformed into β-FeOOH.     

Tris-(salicylaldehydato)-Komplexe einiger Seltenerdelemente mit o-Hydroxybenzoylhydrazid

Complexes of some rare earth elements (La, Ce^III and Y) with salicylaldehyde and o-hydroxybenzoylhydrazide of formula La(o-Bh)₃(Sald)₃·4 H₂O, La(o-Bh)₆(Sald)₃, Ce(o-Bh)₆(Sald)₃, and Y(o-Bh)₅(Sald)₃·2 H₂O were isolated. These complexes were identified by elementary analysis and characterized by X-ray crystallography, thermogravimetric analysis and IR absorption spectroscopy. Coordination sites of o-hydroxybenzoylhydrazide are discussed with reference to the characteristic IR absorption bands of the CONHNH₂ and phenolic OH groups.

---

o-Bh o-Hydroxybenzolhydrazid - Stald Salicylaldehyd     

Über Metall-Stickoxid-Komplexe. XXVI. Nitrosyl-Komplexe von Kobalt und Eisen mit Chelatbildnern

Under replacement of NaBr five- and sixmembered nitrosyl chelat complexes are formed by the reaction of nitrosyl halides of iron and cobalt with sodium salts of acyloines like benzoin and 1,3-diketones such as actylacetone, benzoylacetone and dibenzoylmethane. In the same way react sodium salicylate and pyrocatechol yielding monomeric chelat complexes; by the reaction of disodium pyrocatechol with dinitrosylcobaltbromide a dimeric compound (ON)₂CoOC₆H₄OCo(NO)₂ was found containing oxobridges only. The IR-spectra are discussed.     

Bestimmung einiger pharmazeutischer Wirksubstanzen mit phenolischen Hydroxylgruppen als Eisen(III)-Verbindungen

Zusammenfassung Die Anwendung der Elatographie zur Identifizierung und halbquantitativen Bestimmung organischer, mit Eisen(III)-chlorid farbige Komplexe bildender Substanzen wird beschrieben.

---

Summary The elatographic technique is used for the identification and half-quantitative determination of organic substances, which produce coloured complexes with iron(III)-chloride.

---

---

I. Mitteilung: Becker, A. ¹; II. Mitteilung: Becker, A., u. F. Ehinger ².     

Über Oxidhydroxide des vierwertigen Mangans mit Schichtengitter. 1. Mitteilung. Natriummangan (II,III)manganat(IV)

The preparation of Na₄Mn₁₄O₂₇, 9H₂O (hitherto named manganomanganite or δ-MnO₂) by oxidation of a fresh Mn(OH)₂ suspension in aqueous NaOH by molecular oxygen, and its probable structure are described. It is a double layer manganate (IV) structure resembling other manganates such as chalcophanite. Orthorhombic unit cell parameters are, a₀ = 8,54, b₀ = 15,39, c₀ = 14,26 Å. In diluted nitric acid topotactical transition to manganese (III) manganate (IV), Mn₇O₁₃.5H₂O (unit cell: a₀ = 2,84, c₀ = 7,27 Å; primitively hexagonal), and by prolonged digestion to nsutite, γ-MnO₂, occurs.