Heterodiamantane und strukturell verwandte Verbindungen. III.. Pentacyclische diäther der C11-reihe. 5, 13-Dioxapentacyclo-[6.5.0.02,6.03,12.04,9]tridecan, 4, 13-dioxapentacyclo [6.4.1.02,7.03,10.05,9]tridecan und 3, 10-dioxapentacyclo [7.3.1.02,7.04,12.06,11]tridecan

Heterodiamantanes and Structurally Related Compounds. Part III. The Pentacyclic C₁₁-Diethers 5, 13-Dioxapentacyclo [6.5.0.0^2,6.0^3,12.0^4,9]tridecane, 4, 13-Dioxapentacyclo [6.4.1.0^2,7.0^3,10.0^5,9]tridecane, and 3, 10-Dioxapentacyclo [7.3.1.0^2,7.0^4,12.0^6,11]tridecane In connection with the studies on heterodiamantanes and structurally related compounds the three novel pentacyclic diethers 3 – 5 were prepared starting from the cyclopentadienone dimer 6 . All four compounds have as common features a central carbocyclic 6-membered ring with four axial alkyl substituents and two oxygen functions in 1, 4 position. The required eleventh C-atom was introduced by dichlorocarbene addition either to 6 ( → 7 ) (Scheme 2) or to 29 ( → 28 ) (Scheme 4). Diether 3 was obtained by reduction of 26 (Scheme 2), a suitable precursor prepared either by intramolecular addition ( 24 → 26 ; Scheme 2) or substitution ( 30 → 26 , 31 → 26 ; Scheme 4), as well as by direct substitution ( 44 → 3 , 42 → 3 ; Scheme 5). Diether 4 was the product of a direct substitution ( 39 → 4 , 36 → 4 ; Scheme 5). The synthesis of diether 5 was achieved from the addition product 51 (resulting from the alcohols 47 and 48 ; Scheme 6). Diether 4 is the thermodynamically least stable of the three diethers 3 – 5 . It was easily isomerized to 5 on treatment with concentrated sulfuric acid in benzene whereas 3 and 5 remained unchanged under these conditions.     

Thiosilicate der Selten‐Erd‐Elemente: I. Die isotypen Verbindungen KCe[SiS4] und Eu2[SiS4]

Thiosili‐Thiosilicates of the Rare‐Earth Elements: I. The Isotypic Compounds KCe[SiS₄] and Eu₂[SiS₄] Both isotypic thiosilicates KCe[SiS₄] (a = 649.15(6), b = 656.18(6), c = 863.96(8) pm, β = 107.531(9)°) and Eu₂[SiS₄] (a = 651.71(6), b = 659.54(6), c = 821.93(8) pm, β = 108.437(9)°) crystallize monoclinically in the space group P2₁/m and Z = 2. By the reaction of KCl, Ce₂S₃ and SiS₂ in the ratio 1 : 1 : 1 using a sixfold molar amount of KCl as flux in evacuated silica tubes (7 d, 850°C) brownish yellow, plate‐shaped single crystals, resistant both to air and water are obtained. The conversion of Eu, S and SiS₂ in molar ratios of 2 : 2 : 1 with an excess of CsCl as flux in evacuated silica tubes (7 d, 850°C) leads to deep red, plate‐shaped single crystals, which remain air‐ and water‐stable for a few days. The crystal structure contains isolated ortho‐thiosilicate units, that together with the Ce³⁺ or (Eu2)²⁺ cations build corrugated anionic layers parallel (001) according to {(Ce[SiS₄])^—} and {(Eu2[SiS₄])^2—}, respectively. These layers are alternatingly piled with cationic layers consisting solely of K⁺ or (Eu1)²⁺ cations. The latter show coordination numbers of eight in the shape of a bicapped trigonal prism, whereas the cations of the position Ce³⁺ and (Eu2)²⁺ have a (2+1)‐fold capped trigonal prismatic environment with a coordination number of 8+1. The comparison of both compounds KCe[SiS₄] and Eu₂[SiS₄] (≡ EuEu[SiS₄]) demonstrates, that Eu²⁺ is able to substitute both K⁺ and Ce³⁺ isomorphically.     

Untersuchungen über das Verhalten organischer Mischphasen 9. Mitteilung Vergleich der binären Systeme Tetrahydrofuran mit Wasser,Methanol und Cyclohexan,Diäthyläther mit Wasser,Methanol und Cyclohexan und Tetrahydrofuran-Diäthyläther

Activities and mixing functions of the following binary systems at 25° C are discussed: 1. mixtures of tetrahydrofuran with water, methanol, and cyclohexane; 2. mixtures of diethyl ether with water, methanol, and cyclohexane, and 3. mixtures of tetrahydrofuran with diethyl ether. Comparison with similar systems shows that in systems containing methanol, the strongest interactions are formation and breaking of hydrogen bonds between alcohol molecules; interactions between methanol and ether molecules play a minor rǒle. Systems containing water exhibit two main kinds of interaction: formation and breaking of hydrogen bonds between water molecules, and formation of hydrogen bonds between water and ether molecules. Deviations from ideality are larger for diethyl ether than for tetrahydrofuran in water and methanol, and smaller in cyclohexane.     

Stereochemie von Metallocenen, 33. Mitt.: Optisch aktive Aryl-ferrocene, 4. Mitt.: Optisch aktive Ferroceno[b]indene,-hydrindene und verwandte Verbindungen

Zusammenfassung Optisch aktives Ferroceno[b]indenon (2) wurde durch kinetische Racematspaltung des gut zugänglichenendo-Ferroceno-indenols3 mit (+)--Phenylbuttersäure-anhydrid in optischen Ausbeuten um 20% erhalten. Aus den Ergebnissen dieser Racematspaltung (auch für dasexo-Carbinol5) ließen sich auf Grund der bekannten Absolutkonfiguration (+)-(1R)-2 die relativen stereochemischen Größen von Ferrocen und Benzol (Fc>Phenyl) erstmals festlegen.Mehrere Folgeprodukte von (+)-2 (darunter Ferrocenohydrindene) wurden dargestellt und ihre chiroptischen Eigenschaften mit jenen von strukturell verwandten Ferrocenderivaten (wie13–18) verglichen (und diskutiert). DieCD-Kurven wurden einer Bandenanalyse unterworfen.

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Stereochemistry of metallocenes, XXXIII. (ferrocenes, LIV). Optically active arylferrocenes, IV: Optically active ferroceno[b]indenes, hydrindenes, and related compounds

Optically active ferroceno[b]indenon (2) was obtained by kinetic resolution of the easily accessibleendo ferroceno indenol (3) with (+)--phenylbutyric anhydride with optical yields of 20%. From the results of this resolution (also for theexo-carbinol5) on the basis of the known absolute configuration (+)-(1R)-2 the relative stereochemical sizes of ferrocene and benzene could be established for the first time:Fc>phenyl.Several subsequent products of (+)-2 (amongst them ferroceno hydrindenes) were prepared and their chiroptical properties compared with those of structurally related ferrocenes (such as13–18) (and discussed). TheCD-curves were subjected to a band analysis.

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Mit 6 Abbildungen

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Herrn Prof. Dr.M. Pailer in herzlicher Verbundenheit zum 60. Geburtstag gewidmet.

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32. Mitt. (3. Mitt. über optisch aktive Aryl-ferrocene, 53. Mitt. über Ferrocenderivate):H. Falk, H. Lehner undK. Schlögl, Mh. Chem.101, 967 (1970).     

Verbindungen der L-Ascorbinsäure mit Metallen. II. Titanylascorbate

Compounds of L-Ascorbic Acid with Metals. II. Titanyl Ascorbates The titanyl ascorbates TiO(C₆H₇O₆)₂ · 2 H₂O and TiO(OH)(C₆H₇O₆) the preparation of which has been described elsewhere are characterized by electronic, infrared, and ¹H-nmr spectra. From measurements of the H₃O⁺ concentration of aqueous solutions of both compounds a simple model for describing their protolytic behaviour is derived.     

Strukturverwandtschaften zwischen trigonalen Verbindungen mit hexagonal-dichtester Anionen-Teilstruktur und besetzten Oktaederlücken. Berechnung der Anzahl möglicher Strukturtypen. II [1]

Structural Relations among Trigonal Compounds with Hexagona Closest-packing of Anions and Occupied Octahedral Voids. Calculation of the Numbers of Possible Structure Types, 2^nd Communication [1] The unit cell of the hexagonal closest-packing is enlarged trifold and trigonal symmetry is retained. When part of the octahedral voids are then occupied, several known crystal structure types result. The crystallographic group-subgroup relations are shown. For each of the space groups the number of possible independent structure types is calculated according to chemical composition. Known representatives include RhF₃, corundum, ilmenite, LiNbO₃, BiI₃, WCl₆, LiSbF₆, Na₃GdCl₆, and Li₂ZrF₆; distorted varieties are RuBr₃, PI₃ and N(CH₃)₃. No representative is known for one possible structure type for compounds MX₃ in the space group R32; it could be adopted by WCl₃ and contains pairs of face-sharing octahedra linked by common vertices.     

Bildung siliciumorganischer Verbindungen. LX. Die Kristall- und MolekülStruktur des Heptamethyl-tetrasila-[2,2,2]-barrelans Si4C11H28

Formation of Organosilicon Compounds. LX. Crystal and Molecular Structure of Heptamethyl-tetrasila-[2,2,2]-barrelan Si₄C₁₁H₂₈ 1,1,3,5,5,7,7-Heptamethyl-1,3,5,7-tetrasila-[2,2,2]-barrelan Si₄C₁₁H₂₈ crystallizes in the orthorhombic space group Pn2₁a with a = 12.293, b = 9.903, c = 14.018 Å and Z = 4 formula units. The six-membered rings have the skew-boat conformation with a torsion angle of 23.5° with respect to the molecular axis. The skew-boat conformation results from the interaction of CH₃- and CH₂- groups. The mean value for the bond length is Si? C = 1.881 Å. The distances Si? CH₂ = 1.873 Å are somewhat smaller than the others (1.887 Å).     

Hydroxoverbindungen. 10. Über die Natriumoxohydroxostannate(II) Na4[Sn4O(OH)10] und Na2[Sn2O(OH)4]

Hydroxo Compounds. 10. The Sodium Oxohydroxostannates(II) Na₄[Sn₄O(OH)₁₀] and Na₂[Sn₂O(OH)₄] Na₄[Sn₄O(OH)₁₀] = Na₄[Sn(OH)₃]₂[Sn₂O(OH)₄] ( I ) and Na₂[Sn₂O(OH)₄] ( II ) have now been doubtlessly characterized as the first Na-hydroxostannates(II). I crystallizes monoclinic in P2₁/n (a = 1522.4(5) pm, b = 830.0(2) pm, c = 1276.0(3) pm, β = 104.8(2)°, Z = 4, R = 0.047, 1137 I_hkl); II crystallizes orthorhombic in P2₁2₁2₁ (a = 1450(2) pm, b = 1665(2) pm, c = 590.7(8) pm, Z = 8, R = 0.042, 1208 I_hkl). II is identical with the compound which was described up to now as “Na[Sn(OH)₃]”. The new compounds contain the complex anions [Sn(OH)₃]^? and [Sn₂O(OH)₄]^2?, whose structures are now proved. The oxotetrahydroxo-distannate(II) anion [Sn₂O(OH)₄]^2? exhibits a syn-conformation with respect to the projection along the (Sn? Sn) vector. The two compounds crystallize with pronounced layer structures, which show direct topotactical relations with one another as well as with SnO. This relates closely to the fast formation of SnO from crystals of I and II .     

Raman- und infrorofspektroskopische Untersuchungen on Alkylderivaten der Arsensäure. V1 Die Schwingungsspektren der Dimethyl- und Diäthylarsinsäure sowie deren Reaktionsprodukte mit Chlorwasserstoff

RAMAN and IR Spectroscopic Investigation on Alkyl Derivatives of Arsenic-Acid. V. Vibrational Spectra of Dimethyl and Diethyl Arsinic Acid and their Reaction Products with HCl The RAMAN and IR spectra of (CH₃)₂AsO₂H–partially deuterated–and (C₂H₅)₂AsO₂H and of the reaction products of these acids with HCl (solid and in concentrated aqueous solution) are discussed. The symmetry of the R₂AsO₂H skeleton is C_s. of the [R₂As(OH)₂]+ ion very probably C_2v. Whereas (CH₃)₂AsO₂H gives with HCl only a compound (CH₃)₂ACO₂H · HCl (connected by H bonds), the weaker (C₂H₅)₂AsO₂H is able to form a salt [(C₂H₅)₂As(OH)₂]Cl. The H bonds in the substances are discussed.     

Ternäre Verbindungen des Lithiums und Natriums mit Mangan und Elementen der 5. Hauptgruppe

Es wird über Darstellung und Kristallstruktur ternärer AMnX-Verbindungen (A ? Li, Na; X ? P, As, Sb, Bi) berichtet. Sie kristallisieren tetragonal in Raumgruppe P4/nmm-D_4h⁷, wobei sich LiMnX und NaMnX durch unterschiedliche Punktlagen der Alkaliatome unterscheiden. Die AMnX-Strukturen werden mit denen verwandter AMX-Verbindungen verglichen (A ? Li, Na, K, Rb; M ? Be, Mg, Zn, Cd; X ? 5b-Element). Ternary Compounds of Lithium and Sodium with Manganese and Elements of the Fifth Main Group Formation and crystal structure of ternary AMnX compounds (A ? Li, Na; X ? P, As, Sb, Bi) are reported. These compounds crystallize in the tetragonal space group P4/nmm-D. The structures of LiMnX and NaMnX differ by the positions of the alkali atoms. Structural relationship to AMX compounds (A ? Li, Na, K, Rb; M ? Be, Mg, Zn, Cd; X ? 5b element) are discussed.     

Metallorganische Verbindungen der Lanthanoide. 111. Synthese und Charakterisierung kationischer Metallocen-Komplexe der Lanthanoide. Röntgenstrukturanalyse von [CpYb(THF)2][BPh4]

Organometallic Compounds of the Lanthanoids. 111. Synthesis and Characterization of Cationic Metallocene Complexes of the Lanthanoides. X-Ray Crystal Structure of [Cp Yb(THF)₂][BPh₄] Cationic organolanthanoide compounds [(C₅H₄R)₂Sm(THF)₂][BPh₄] (R = ^tBu ( 1 ), SiMe₃ ( 2 )), [PyrSm(THF)][BPh₄] ( 3 ) (Pyr* = NC₄H₂^tBu₂-2,5), [CpLn(THF)₂][BPh₄] (Cp* = C₅Me₅; Ln = Y ( 4 ), Yb ( 5 )), and [(C₅Me₄Et)₂ Ln(THF)₂][BPh₄] (Ln = Y ( 6 ), Sm ( 7 )) have been synthesized by oxidation of the divalent metallocenes [(C₅H₄R)₂Sm(THF)₂] (R = ^tBu, SiMe₃), [PyrSm(THF)], [CpYb(THF), and [(C₅Me₄Et)₂Sm(THF)] with Ag[BPh₄] and by protolysis of the lanthanoide alkyls [CpYMe(THF)], [CpYbCH(SiMe₃)₂], and [(C₅Me₄Et)₂LnCH(SiMe₃)₂] (Ln = Y, Sm) by [NEt₃H][BPh₄]. The ¹H- and ¹³C-NMR spectra of the new compounds are discussed. 5 crystallizes in the space group P2₁/c with a = 10.604(7), b = 21.749(3), c = 19.124(4) Å, β = 96.47(4)°, Z = 4 and V = 4383(3) ų (R = 0.0291 for 8517 observed reflections with F_o ≥ 4σ (F_o).     

Metallorganische Verbindungen der Lanthanoide. 155 [1] Synthese und Charakterisierung neuer Lanthanoidocen‐Komplexe mit silylierten Cyclopentadienylliganden

Organometallic Compounds of the Lanthanides. 155 [1] Synthesis and Characterization of New Lanthanocene Complexes containing Silylated Cyclopentadienyl Ligands The trichlorides of yttrium, samarium, and lutetium react with two equiv. of K[C₅H₄SiEt₃] ( 1 ) to form the dimeric compounds [(η⁵‐C₅H₄SiEt₃)₂LnCl]₂ (Ln = Y ( 2 ), Sm ( 3 ), Lu ( 4 )). These react with one equiv. of methyllithium to give the corresponding dimeric lanthanocenemethyl complexes [(η⁵‐C₅H₄SiEt₃)₂LnMe]₂ (Ln = Y ( 5 ), Sm ( 6 ), Lu ( 7 )). The reaction between samarium trichloride and lutetium trichloride, respectively with two equiv. of K[1, 3‐C₅H₃(SiMe₃)₂] followed by one equiv. of methyllithium results in the formation of the monomeric methyl complexes [η⁵‐1, 3‐C₅H₃(SiMe₃)₂]₂LnMe(THF) (Ln = Sm ( 8 ), Lu ( 9 )). The new compounds have been characterized by elemental analysis, mass spectrometry, ¹H‐ and ¹³C{¹H} NMR spectroscopy, as well as 1 — 7 by single crystal X‐ray structure analysis.     

Thiosilicate der Selten‐Erd‐Elemente: III. KLa[SiS4] und RbLa[SiS4] – Ein struktureller Vergleich

Thiosilicates of the Rare‐Earth Elements: III. KLa[SiS₄] and RbLa[SiS₄] – A Structural Comparison Pale yellow, platelet shaped, air‐ and water resistant single crystals of KLa[SiS₄] derived from the reaction of lanthanum (La) and sulfur (S) with silicon disulfide (SiS₂) in a molar ratio of 2 : 3 : 1 with an excess of potassium chloride (KCl) as flux and source of potassium ions in evacuated silica ampoules at 850 °C within seven days. The analogous reaction utilizing a melt of rubidium chloride (RbCl) instead also leads to yellow comparable single crystals of RbLa[SiS₄]. The potassium lanthanum thiosilicate crystallizes monoclinically with the space group P2₁/m (a = 653.34(6), b = 657.23(6), c = 867.02(8) pm, β = 107.496(9)°) and two formula units per unit cell, while the rubidium lanthanum thiosilicate has to be assigned orthorhombically with the space group Pnma (a = 1728.4(2), b = 667.23(6), c = 652.89(6) pm) and four formula units in its unit cell. In both compounds the La³⁺ cations are surrounded by 8+1 sulfide anions in the shape of tricapped trigonal prisms. The Rb⁺ cations in RbLa[SiS₄] show a coordination number of 9+2 relative to the S^2? anions, which form pentacapped trigonal prisms about Rb⁺. This coordination number, however, is apparently too high for the K⁺ cations in KLa[SiS₄], so that they only exhibit a bicapped trigonal prismatic environment built up by eight S^2? anions. The isolated thiosilicate tetrahedra [SiS₄]^4? of the rubidium compound are surrounded by La³⁺ both edge‐ and face‐capping, but terminal as well as edge‐ and face‐spanning by Rb⁺. In the potassium compound there is no change for the La³⁺ environment about the [SiS₄]^4? tetrahedra, but the K⁺ cations are only able to attach terminal and via edges. The whole structure is built up by anionic equation/tex2gif-stack-1.gif{La[SiS₄]}^? layers that are separated by the alkali metal cations. In direct comparison the two thiosilicate structures can be regarded as stacking variants.