Über ein spirocyclisches Pentaalkylphosphoran und Alkoxytetraalkylphosphoran,sowie über ein monocyclisches kovalentes Fluorotetraalkylphosphoran

Spirocyclic Pentaalkylphosphorane, Alkoxy tetraalkylphosphorane and a Monocyclic Covalent Fluorotetraalkylphosphorane Methylation of the spiro-phosphonium salt (CH₂)₄P(CH₂)₄⊕Cl? by CH₃Li at ?60°C affords the bicyclic pentaalkylphosphorane , a colourless distillable liquid of characteristic odour. The corresponding bicyclic methoxytetraalkylphosphorane is obtained from the same phosphonium salt with NaNH₃ followed by CH₃OH. The reaction is assumed to occur via the unstable bicyclic ylide. From 1-methyl-1-methylene-phospholane and NH₄F the liquid and distillable, covalent fluorotetraalkylphoshorane (CH₂)P(CH₃)₂F is formed. A complete ¹H-, ¹³C-, ¹⁹F- and ³¹P-NMR study has been carried out for these three compounds. Due to a pronounced fluxional behaviour, none of the fixed standard geometries (TBP, SP) can be assigned.     

Neues über Oxouranate: Über α-Li6UO6. Mit einer Bemerkung über β-Li6UO6

New Investigations about Oxo Uranates: On α-Li₆UO₆. With a Remark about β-Li₆UO₆ The crystal structure of transparent, bright yellow single crystals of α-Li₆UO₆ has been determined. [a = 838.07(5), c = 738.34(7) pm; d_pyk = 4.02, d_x = 4.17 g · cm^?3; space group R3 ; Z = 3; R = 3.17%, R_w = 3.06%; 408 symmetry independent I₀(hkl); AgKα fourcircle diffractometer Philips PW 1100]. The structure is dominated by a threedimensional framwork of “hollow spaces”, built up by 12 O^2? (and 12 Li⁺). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Chaenorhin,ein macrocyclisches Spermin-Alkaloid. 149. Mitteilung über Alkaloide

Structure 1 has been elucidated for chaenorhine, an alkaloid isolated from Chaenorhinum organifolium (Scrophulariaceae). The key derivative for the structural elucidation is 13,14,21,22-tetrahydro-21,22-seco-chaenorhine ( 21 ). 21 gave upon hydrolysis spermine and 4-hydroxydihydrocinnamic acid characterized as the tetraacetyl derivative 18 and as the dimethyl derivative respectively.     

Neues über Zweikernige Oxoferrate(II)

News about Binuclear Oxoferrates(II) [1] . By “reaction with the wall” of the Fe-cylinders used here we synthesized the new oxoferrates(II) Cs₆[Fe₂O₅], Cs_3.5Rb_2.5[Fe₂O₅] and Rb₄K₂[Fe₂O₅] in the form of red single crystals. The structure elucidation via four-circle-diffractometer data shows that the new oxoferrates(II) are isotypic with Cs₂(Cs_0.35K_1.65)K₂ [Fe₂O₅]. In the structure we have isolated binuclear groups [(O1)₂Fe—O(2)—Fe(O1)₂]^6?. Structure refinements is possible in the centrosymmetrial space group C2/m as well as in the space groups C2 and Cm without centre of symmetry. The existence of two further oxoferrates(II) Cs_6?xRb_x[Fe₂O₅] and Cs_6?xK_x[Fe₂O₅] which can be described as solid solutions was confirmed by power-data.     

Über ein neues Oxoiridat(IV): Ba7Ir6O19

Summary The so far unknown compound Ba₇Ir₆O₁₉ was prepared by long time solid state reactions using a flux of BaCl₂. X-ray single crystal work lead to the space group C _2h ³ —C2/m;a=14.913;b=5.778;c=10.979 Å; =99.58°;Z=2. It crystallizes with a new structure type characterized by three face-shared octahedra. The Ir₃O₁₂-groups build up a threedimensional network with an incorporated Ba/O-frame.

     

Über Chalkogenolate, 72. Untersuchungen über Titan(IV)-monomethylcarbonate

New Phases in the System YbF₂? YbF₃ Systematic investigations of the phase relationships in the system YbF₂? YbF₃ resulted into four new compounds: Yb₃F₇, Yb₁₄F₃₃, Yb₂₇F₆₄ und Yb₁₃F_32?δ. These mixed-valence fluorides have anion-excess fluorite-superstructures, which can be described by the homologous series formula Yb_mF_2m+5 (m = 15, 14, (14+13)/2 and 13). According to this formula Yb₂₇F₆₄ can be considered as an ordered intergrowth of Yb₁₄F₃₃ and Yb₁₃F₃₁. Yb₁₃F_32?δ is isostructural with Na₇Zr₆F₃₁. Lattice constants and x-ray powder patterns of all phases are reported.