Branched Star-Type Polysilyllithium Compounds: The Effects of beta-Silyl Substitution and of Complexation on Their Molecular Structure

No Abstract     

Reaktionen an komplexgebundenen liganden: XXXVI. Synthese und oxidationsverhalten von M(CO)5-komplexen (M = Cr,Mo, W) mit amin- und benzochinondiimin-liganden

The oxidation of yellow Cr(CO)₅NH₂R complexes (NH₂R = aniline, m-toluidine, 3,5-xylidine, m-anisidine) with Pbac₄ gives deep blue to deep purple coloured compounds, which have been identified as the respective [Cr(CO)₅(N-phenyl-1,4-benzochinon-diimine)] complexes. Oxidation of the p-phenylenediamine complex yields [(OC)₅CrHNC₆H₄NHCr(CO)₅], which is also deep blue. The binuclear blue complex [{Cr(CO)₅}₂HNC₆H₄NC₆H₅] is obtained by treating Cr(CO)₅THF with the free ligand in THF/hexane; it dissociates rapidly in acetone to form [Cr(CO)₅HNC₆H₄NC₆H₅] and Cr(CO)₅. Analogous Mo(CO)₅ and W(CO)₅ complexes could not be obtained. The oxidation of [W(CO)₅(m-anisidine)] by I₂ yields [W(CO)₄I]₂. All the compounds were characterized by spectroscopic methods as well as by elemental analysis.     

The mass spectra of TMS-ethers of deuterated polyalcohols. A contribution to the structural investigation of sugars

Aldoses, ketoses, deoxy-aldoses, deoxy-keto-aldoses, lactones, deoxy-lactones and other similar compounds are readily reduced by NaBD₄ to the corresponding polyalcohol. Their trimethylsilyl ethers show characteristic mass spectra which allow firm assignments of the position of deuteration and hence of the nature of the starting sugar compound. The g.c./m.s. coupling technique even allows trace analysis since full information can be derived from the most intense fragments of the mass spectra.     

Intramolekulare Cyclisierung von Aminofluorsilanen

Aminofluorosilanes react with lithiated amines undergoing LiF-elimination and substitution (1). The acyclic silicon-nitrogen-compound2 is isolated in the reaction with a difluorosilane after renewed lithiation.2 is cyclisated in the reaction with butyllithium by butane- and LiF-elimination (3). Aminofluorosilanes with bulky (4) or mesomeric stabilized (5) ligands form stable lithioaminofluorosilanes, which react with fluorosilanes giving substitution products (6, 7).6 and7 react with the lithium salt oftert-butylamin in a molar ratio of 12 to give8 and9 by intramolecular cyclisation.—The mass,¹H and¹⁹F nmr spectra of the compounds are reported.     

Synthesis of Naturally Occurring Pyrazine and Imidazole Alkaloids from Botryllus LeachiRID=”a”ID=”a”?Dedicated to Prof. G. M?rkl on the occasion of his 75th birthday

The synthesis of the naturally occurring and biologically active alkaloids 1 and 2, first isolated from the red ascidian Botryllus leachi by Duran et al. [1], is described and the structure proposed for Botryllazine B (1) is confirmed. The analytical data for 2-(p-hydroxybenzoyl)-4-(p-hydroxyphenyl)imidazole (2) are discussed and compared with the literature. With special emphasis of ¹H NMR data the tautomerism of aroylimidazolemethanones is described.     

Syntheses of (+)-(S,S)-(cis-6-Methyltetrahydropyran-2-yl)acetic acid and of (−)-(R,R)-Didesoxy-pyrenophorine Using a New d5-Reagent. Preliminary communication

The Li/K-derivative 6 is used to synthesize the title compounds ( 3a and 4a ) in enantiomerically pure form from (?)-(S)-propylene epoxide. The C,C bond forming key step leading to the hydroxyketone 7 is followed by cyclization (→, 8 ), Beckmann cleavage (→ 9b ) and hydrolysis to 3a (recently isolated from civet). Base treatment of 3a opens the ring ( 10 ) to give the hydroxyacid 1 which is cyclized to the macrolide 4a . The synthetic usefulness of the highly nucleophilic doubly reduced dienone system 6 as d⁵-reagent (see synthons 2) is thus demonstirated.     

A convenient synthesis of 4-aminoaryl substituted cyclic imides

An efficient one-step synthesis of 4-nitro-N-aryl substituted glutarimides, succinimides and maleimides in polyphosphoric acid is described together with the subsequent reduction to the corresponding anilines. The scope and limitation of this cyclocondensation are presented.     

Farbe und Konstitution bei anorganischen Feststoffen, 12. Mitt.: Die Lichtabsorption des zweiwertigen Kobalts in oxidischen Koordinationsgittern vom Ilmenittyp

Zusammenfassung Die Systeme Co _x Mg _1-x TiO₃ (I) und Co _x Cd _1-x TiO₃ (II) wurden röntgenographisch und spektralphotometrisch untersucht. I stellt eine lückenlose Mischkristallreihe dar. Mit wachsendemx nehmen bei I die Gitterkonstantena ₀undc ₀geringfügig zu und die drei Hauptabsorptionsbanden verschieben sich ein wenig in Richtung IR. In II liegt keine lückenlose Mischkristallreihe vor. Sowohl röntgenographisch als auch spektralphotometrisch wurde für die an CoTiO₃ gesättigte CdTiO₃-Phase die Zusammensetzung Co_0,3Cd_0,7TiO₃ (II a) und für die an CdTiO₃ gesättigte CoTiO₃-Phase die Zusammensetzung Co_0,8Cd_0,2TiO₃ (II b) gefunden.Beim Übergang III (x=0,1) wird eine beträchtliche IR-Verschiebung beobachtet. Die IR-Verschiebung ist die Folge der Gitteraufweitung bei der Substitution von Mg²⁺ durch Cd²⁺. Hierbei nimmt derRacah-Parameter geringfügig zu infolge Verminderung der covalenten Anteile der Bindung Co-O.

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The systems Co _x Mg _1-x TiO₃ (I) and Co _x Cd _1-x TiO₃ (II) had been investigated spectrophotometrically and by X-ray diffraction. I represents mixed crystals without any miscibility gap. An increase ofx causes a small enhancement of the lattice unitsa ₀andc ₀of I and the three main absorption bands will be shifted slightly towards IR. II are mixed crystals with a broad miscibility gap. Spectrophotometrically and by X-ray diffraction it could be found that the CdTiO₃-phase saturated with CoTiO₃ and the CoTiO₃-phase saturated with CdTiO₃ have the compositions Co_0,3Cd_0,7TiO₃ (II a) and Co_0,8Cd_0,2TiO₃ (II b), respectively. The transition III (x=0,1) produces a considerable shift of the main absorption bands towards IR as a consequence of the expansion of the lattice caused by the substitution of Cd²⁺ for Mg²⁺. This shift is accompanied by a small increase of theRacah-Parameter owing to a decrease of covalency of the bonding Co-O.

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11. Mitt.:D. Reinen, Mh. Chem.96, 730 (1965).     

First successful reaction of a silyl anion with hafnium tetrachloride

Hafnium tetrachloride reacts with the tris(trimethylsilyl)silyl potassium tmen adduct (1) to form a [tris(trimethylsilyl)silyl]trichlorohafnium tmen complex (2); reaction of 2 with 2,6-dimethylphenylisonitrile leads to insertion into the silicon hafnium bond (4).     

Übergangsmetallphosphidokomplexe. VIII. Strukturuntersuchungen an Übergangsmetallphosphor-Vier- und Sechsringkomplexen. Die Strukturen von [(CO)4MnPH2]2, [(CO)4MnPH2]3 und [cpNiPH2]3

Transition Metal Phosphido Complexes. VIII. X-Ray Diffraction Studies of Transition Metal Phosphorus Four- and Six-Membered Ring Complexes. Structures of [(CO)₄MnPH₂]₂, [(CO)₄MnPH₂]₃, and [cpNiPH₂]₃ [(CO)₄MnPH₂]₂ 1 crystallizes triclinic in the space group P1 with a = 680.4 pm, b = 706.4 pm, c = 919.1 pm, α 110.5°, β = 91.92°, γ 115.65°, and Z = 1 formula unit. The molecule exhibits a centrosymmetrical structure. The bond angles within the planar four-membered (Mn? P)₂-ring are 76.1° at the Mn atoms and 103.9° at the P atoms, respectively. The average Mn? P bond distance is found to be 235.1 pm. [(CO)₄MnPH₂]₃ 2 crystallizes monoclinic in the space group P2/n with a = 905.2 pm, b = 974.8 pm, c = 1264.2 pm, β = 109.1°, and Z = 2 formula units. The framework of the six-membered (Mn? P)₃-ring can be described as having a twist boat conformation. The average endocyclic bond angles are with 89.1° at the Mn atoms and 130.1° at the P atoms, respectively, largely widened compared to 1 . The average Mn? P bond distance, which is found to be 238.5 pm, is also slightly increased compared to 1 . [cpNiPH₂]₃ 3 crystallizes rhombohedral in the space group R3. The cell constants (hexagonal setting) are a = b = 1686.1 pm, c = 561.1 pm and Z = 3 formula units. The six-membered (Ni? P)₃-ring exhibits a chair conformation. The endocyclic bond angles are with 92.3° at the Ni atoms and 124.3° at the P atoms, respectively, comparable with those of the six-membered ring compound 2 . The Ni? P bond distance is found to be 215.2 pm. The eyclopentadienyl ligands are disordered and have been refined as rigid groups.