Ferrocene compounds. XXXIX.

In the title compound, [Fe(C₅H₅)(C₁₄H₁₃O)], the plane of the heterocyclic ring is almost perpendicular to the plane of the substituted cyclo­penta­dienyl ring, and the heterocyclic ring adopts a half‐chair conformation. The conformation of the nearly parallel cyclo­penta­dienyl (Cp) rings [the dihedral angle between their planes is 2.7 (1)°] is almost halfway between eclipsed and staggered, and the rings are mutually twisted by about 19.4 (2)° (mean value). The mean lengths of the C—C bonds in the substituted and unsubstituted cyclo­penta­dienyl ring are 1.420 (2) and 1.406 (3) Å, respectively, and the Fe—C distances range from 2.029 (2) to 2.051 (2) Å. The phenyl and unsubstituted cyclo­penta­dienyl rings are involved in C—H⃛π interactions, with intermolecular H⃛centroid distances of 2.85 and 3.14 Å for C—H⃛π(Ph), and 2.88 Å for C—H⃛π(Cp). In two of these interactions, the C—H bond points towards one of the ring bonds rather than towards the ring centroid. In the crystal structure, the C—H⃛π interactions connect the mol­ecules into a three‐dimensional framework.     

Metallorganische verbindungen der lanthanoide : XI. Dicyclopentadienyllutetiumhydrid

Di-η⁵-cyclopentadienyltrimethylsilylmethyllutetium as well as di-η⁵-cyclopentadienylbenzyllutetium react with hydrogen at elevated pressure yielding di-η⁵-cyclopentadienyllutetium hydride, which can be prepared also from di-η⁵-cyclopentadienylchlorolutetium and sodium hydride.     

Funktionelle Monomere und Polymere. 8. Mitt

Ohne Zusammenfassung     

Metallorganische Verbindungen

Ohne Zusammenfassung     

Metallorganische Verbindungen

Ohne Zusammenfassung     

Metallorganische verbindungen der lanthaniden. : III. Dicyclopentadienyllanthanid-triphenylgermane bzw.-stannane

Dicyclopentadienyl-erbium and -ytterbium chloride react with lithium triphenyl-germane or -stannane under formation of dicyclopentadienylerbiumtriphenylgermane, -triphenylstannane and dicyclopentadienylytterbium-triphenylstannane.     

Metallorganische verbindungen der lanthanoiden: XX. Cyclopentadienyllutetiumderivate von triphenylmethylenphosphoran

Tricyclopentadienyllutetium tetrahydrofuranate reacts with triphenylmethylenephosphorane with the formation of tricyclopentadienyllutetium triphenylmethylenephosphorane. A lutetium-containing metallacycle, 1,1-diphenyl-3,3-dicyclopentadienyl-1-phospha-3-luteto-indane, is formed by the decomposition of dicyclopentadienyl(methyl)lutetium triphenylmethylenephosphorane, by the reaction of dicyclopentadienylchlorolutetium triphenylmethylenephosphorane with sodium hydride or by the reaction of dicyclopentadienyllutetium chloride with lithium triphenylphosphonium methylide, respectively. The ¹H and ¹³C NMR spectra of the new compounds are discussed.     

Bildung siliciumorganischer Verbindungen. XXXIX. Teilchlorierte Carbosilane

1. Photochlorination in CCl₄ of the Si-chlorinated carbosilanes (Cl₃Si? CH₂)₂SiCl₂ and (Cl₂Si? CH₂)₃ leads to totally chlorinated compounds, e. g. (Cl₃Si? CCl₂)₂SiCl₂. After chlorination has started at one CH₂ group, formation of a CCl₂ group is preferred before another CH₂ group is involved into the reaction. Thus preparation of compounds a, b, c is possible. Cl₃Si? CCl₂? SiCl₂? CH₂? SiCl₃ (a) for (b) and (c) (see “Inhaltsübersicht”). SO₂Cl₂ (benzoyl peroxide) as chlorinating agent reacts more slowly, and opens an access to carbosilanes containing CHCl groups such as (d), Cl₃Si-CHCl? SiCl₂? CH₂? SiCl₃ (e). Reactions of compounds (a) to (d) with LiAlH₄ yields carbosilanes with SiH groups, and partially chlorinated C atoms. 2. By the high reactivity of Si? CCl₂? Si groups an exchange of Cl atoms of CCl groups in perchlorinated carbosilanes is possible for H atoms of Si? H groups in perhydrogenated carbosilanes, thus allowing the preparation of compounds containing CHCl and SiHCl groups, e. g. according to Gl.(1) (Inhaltsübersicht). Further reactions, formulated as the last equations in Inhaltsübersicht, are reported as well as the rearrangement of H₃Si? CHCl? SiH₃.     

Bildung siliciumorganischer Verbindungen. XXX. Metallorganische Synthese cyclischer Carbosilane

This paper contains:

• 1 The synthesis of the 1.3-disilacyclopentenes (a)(b)⁽²⁾ and of the 1.3-disilacyclo-butane (c); formulas see above.
• 2 The synthesis of the 1.3-disilacyclopentane skeleton (d) and of the SiCl-functional derivatives (e) (f ) (g) (h) (i) as well as of SiH-containing derivatives, e.g. (j).
• 3 The chlorination of (i) with SO₂,Cl₂, yielding (k) and (l), and the formation of (m) from (k) with K-methypyrrolidine.
• 4 The synthesis of the spirane (n).
• 5 The synthesis of the ten-membered ring(o) and of the unsaturated derivatives (p)and (q). Besides the synthetic routes, spectroscopic data (ir, pmr, and mass spectra) of the cyclic compounds as well as of the intermediate products are given.

     

Das restliche Monomere in Polymethylmethacrylat

Ohne Zusammenfassung     

Monomere Tripod–Zink-Thiolat-Komplexe

Monomeric Tripod–Zinc Thiolate Complexes Reaction of the pyrazolylborate-zinc complex Tp^Cum,MeZn–OH with the corresponding thiols yielded the stable complexes Tp^Cum,MeZn–SR ( 1 : R = Ph, 2 : R = CH₂–Ph, 3 : R = CH₂–CH₂–Ph) which are further representatives of this class of compounds. Using the ligand tris(benzimidazolylmethyl)amine (BIMA), zinc perchlorate, and the corresponding sodium thiolates, the cationic complexes (BIMA)Zn–SR (R = Ph, CH₂Ph) were obtained, which were isolated as [(BIMA)Zn–S–Ph] BPh₄ ( 4 ) and [(BIMA)Zn–S–CH₂Ph] ClO₄ ( 5 ). A structure determination of 4 confirmed the pseudotetrahedral coordination geometry for this new type of compounds.     

Monomere und dimere hochhalogenierte Iminoborane

Zusammenfassung Hochhalogenierte monomere Iminoborane bilden sich bei der Reaktion von HCN mit BBr₃ und von Trichloracetonitril mit Trihalogen- bzw. Organohalogen-boranen. Die Verbindungen liegen teilweise im Gleichgewicht mit den entsprechenden tetrakoordinierten Dimeren vor. Aus Pentafluorbenzonitril und RBBr₂ (R=Br, CH₃ oder C₆H₅) gebildete Bis(iminoborane) ergeben bei der Vakuumsublimation die Addukte C₆F₅CN·B(R)Br₂. Aus Halogencyanen und (CH₃)₂BBr gebildete Bis(iminoborane) geben bei der Destillation monomere Iminoborane, welche sich wieder dimerisieren, wie IR-Spektren und Molgewichtsbestimmungen zeigen.

---

Monomeric highly halogenated iminoboranes result from the reaction of HCN with BBr₃ or from trichloroacetonitrile with trihalogeno- and organohalogeno-boranes, respectively. The compounds partly are in equilibrium with the corresponding tetra-coordinated dimers. Bis(iminoboranes) resulting from C₆F₅CN and RBBr₂ (R=Br, CH₃ or C₆H₅) on sublimation in vacuo, yield adducts C₆F₅CN·B(R)Br₂ while bis(iminoboranes) from halogenocyanides and (CH₃)₂BBr yield monomeric iminoboranes on distillation. According to IR spectra and molecular weight determinations the latter redimerize on standing.

---

---

Mit 3 Abbildungen     

Berberis alkaloids XXXIX. New alkaloids fromB. densiflora

The alkaloid composition of the leaves ofBerberis densiflora has been studied. Berberine, -allocryptopine. oxyacanthine, glaucine, thalicmidine, isocorydine, O-methylcorypalline and the new bases densinine and densiberine have been isolated. The structures of the new alkaloids have been established by a study of spectral characteristics and chemical transformations. This is the first time that any of the known alkaloids, apart from berberine, have been isolated from a plant of this pecies and it is the first time that -allocryptopine and O-methylcorypalline have been isolated from theBerberis genus.     

Metallorganische verbindungen der lanthanoiden: XVI. Dicyclopentadienyl(alkyl)lutetinyl-methylentriorganophosphorane

Dicyclopentadienyl(t-butyl)lutetium tetrahydrofuranate and dicyclopentadienyl-(trimethylsilylmethyl)lutetium tetrahydrofuranate react with triphenyl methylenephosphorane and trimethyl (trimethylsilyl)methylenephosphorane in toluene with exchange of the tetrahydrofuran ligand for the ylide and formation of new dicyclopentadienyl(alkyl)lutetinyl methylene triorganophosphoranes. The new zwitterionic complexes (C₅H₅)₂Lu(t-C₄H₉)CH₂P(C₆H₅)₃. (C₅H₅)₂Lu(CH₂SiMe₃)-CH₂P(C₆H₅)₃ and (C₅H₅)₂Lu(t-C₄H₉)CH(SiMe₃)P(CH₃)₃ have been isolated and characterized by their NMR spectra.     

Studies in qualitative inorganic analysis. part XXXIX

Summary A virtually specific test for vanadium(V) is described which, in particular, permits the detection of vanadate in the presence of chromate and molybdate. The behaviour of vanadate in the anion separation scheme of the MAQA scheme of qualitative analysis has been investigated.

---

Zusammenfassung Ein praktisch spezifischer Nachweis von Vanadin(V) wurde beschrieben, womit vor allem Vanadat in Gegenwart von Chromat und Molybdat nachgewiesen werden kann. Das Verhalten von Vanadat im Anionentrennungsgang der MAQA¹ wurde untersucht.

---

---

Part XXXVIII, Mikrochim. Acta [Wien]1969, 1097.     

Enamines—XXXIX : Enamines from cyclopropylketones

The enamines from cyclopropyl-methyl-, -ethyl- and -cyclopentylketone have been prepared by reaction of the ketone with a secondary amine and TiCl₄. Their vinylcyclopropane structure has been demonstrated by NMR. The reaction of dicyclopropylketone, cyclopropylphenylketone or cyclopropyl-α-thienylketone with secondary amines and TiCl₄ afforded homoallylic rearrangement products, namely 1-cyclopropyl-, 1-phenyl- and 1-(α-thienyl)-1,4-diamino-1-butene, respectively.