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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1599-1608 
    ISSN: 0044-2313
    Keywords: Cyclophosphazenes ; [3]ferrocenophanes ; 1,1′-ferrocene-dichalcogenato compounds ; NMR spectra ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Ferrocenol and 1,1′-Ferrocendiol with Cyclotriphosphazenes, P3N3F6 and P3N3Cl6The hexahalogeno-cyclotriphosphazenes, P3N3X6 (X = F (1 a), Cl (1 b)), react with ferrocenol (FcOH) in a molar ratio 1 : 1 to give the ferrocenoxy derivatives, FcO[P3N3X5] (X = F (3 a), Cl (3 b)); in an analogous manner the tetrameric ring P4N4Cl8 (2 b) is converted to FcO[P4N4Cl7] (4 b). Abkürzungen: Fc = Ferrocenyl, (C5H5)Fe(C5H4-); fc = 1,1′-ferrocendiyl, Fe(C5H4-)2; rc = 1,1′-ruthenocendiyl, Ru(C5H4-)2. Fluorphosphazene werden mit a, Chlorphosphazene mit b gekennzeichnet. With 1,1′-ferrocenediol, (fc(OH) 2), the cyclo triphosphazenes react in a molar ratio 1 : 1 to produce fcO 2[P 3 N 3 X 4] (X = F ( 5 a), Cl ( 5 b)). According to the x-ray structure analysis, the 1,1′-ferrocenediolato group in 5 a , b is bound to two different phosphorus atoms. On the contrary, the 1,1′-ferrocenedithiolato- and 1,1′-ferrocenediselenolato units in fcS 2[P 3 N 3 X 5] (X = F ( 6 a), Cl ( 6 b)) and fcSe 2[P 3 N 3 X 5] (X = F ( 7 a), Cl ( 7 b)) are attached to only one phosphorus atom, and spirocyclic 1,3-dichalcogena-2-phospha-[3]ferrocenophanes are formed. All new products have been characterized on the basis of their 1 H, 13 C and 31 P NMR as well as EI mass spectra. The molecular structures of 5 a , b and 6 a have been determined by x-ray structure analyses.
    Notes: Die Hexahalogen-cyclotriphosphazene, P3N3X6 (X = F (1 a), Cl (1 b)), reagieren mit Ferrocenol, FcOH, im Molverhältnis 1 : 1 unter Bildung der Ferrocenoxy-Derivate FcO[P3N3X5] (X = F (3 a), Cl (3 b)); der tetramere Ring P4N4Cl8 (2 b) bildet in analoger Weise FcO[P4N4Cl7] (4 b). 1,1′-Ferrocendiol, fc(OH)2, setzt sich mit P3N3X6 im Molverhältnis 1 : 1 zu fcO2[P3N3X4] (X = F (5 a), Cl (5 b)) um; nach der Röntgenstrukturanalyse ist der 1,1′-Ferrocendiolato-Rest in 5 a, b an zwei verschiedene Phosphoratome gebunden. Dagegen werden die 1,1′-Ferrocendithiolat- und 1,1′-Ferrocendiselenolat-Reste in fcS2[P3N3X4] (X = F (6 a), Cl (6 b)) bzw. fcSe2[P3N3X4] (X = F (7a), Cl (7 b)) jeweils nur an ein Phosphoratom angekoppelt, so daß spirocyclische 1,2-Dichalkogena-2-phospha[3]ferrocenophane entstehen. Alle neuen Produkte wurden anhand ihrer 1H-, 13C- und 31P-NMR-Spektren und der EI-Massenspektren charakterisiert; für 5 a, b und 6 a wurde die Molekülstruktur durch Röntgenstrukturanalyse bestimmt.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 545-553 
    ISSN: 0044-2313
    Keywords: Cyclotetraphosphazenes ; [3]ferrocenophanes ; NMR spectra ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,1′-Ferrocene Dichalcogenato Derivatives of Octachloro-cyclotetraphosphazeneMononuclear 1,1′-ferrocenedichalcogenato derivatives of octachloro-cyclotetraphosphazene, fcE2[P4N4Cl6] (E = O (12), S (13), Se (14), have been prepared and characterized by 1H, 13C and 31P NMR spectroscopy as well as mass spectrometry.1) The molecular structures of 12--14 were determined by X-ray crystallography. While the 11′-ferrocene diolato complex, fcO2[P4N4Cl6] (12), possesses a 1,3-transannular bridged structure, the dithiolato and diselenolato analogues, 13 and 14, are spiro compounds containing 1,3-dichalcogena-2-phospha-[3]ferrocenophane rings. According to their temperature-dependent NMR spectra, 13 and 14 are nonrigid molecules above room temperature in solution.
    Notes: Es wurden einkernige 1,1′-Ferrocendichalkogenato-Derivate des Oktachlor-cyclotetraphosphazens, fcE2[P4N4Cl6] (E = O (12), S (13), Se (14), dargestellt und mit Hilfe der 1H-, 13C- und 31P-NMR-Spektroskopie sowie der Massenspektrometrie charakterisiert.1) Die Molekülstrukturen von 12-14 wurden durch Röntgenstrukturanalysen bestimmt. Während der 1,1′-Ferrocendiolato-Komplex, fcO2[P4N4Cl6] (12), eine 1,3-transannular verbrückte Struktur besitzt, sind die Dithiolato- und Diselenolato-Analoga, 13 und 14, Spiroverbindungen mit l,3-Dichalkogena-2-phos pha-[3]ferrocenophan-Ringen. Entsprechend den temperaturabhängigen NMR-Spektren sind 13 und 14 oberhalb Raumtemperatur in Lösung nichtstarre Moleküle.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0044-2313
    Keywords: Th2Ta6O19 ; LaNb7O19 ; chemical transport ; crystal structure ; “Jahnberg-structure-family” ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of Th2Ta6O19, the First Example of a “Jahnberg-Structure” with M = M4+ (M = Th4+); with a Note to LaNb7O19Colorless, hexagonal crystals of Th2Ta6O19 were obtained by chemical transport in the temperature gradient 1000°C → 980°C using a mixture of ThO2, ZrO2 (or HfO2) and Ta2O5 (1 : 2 : 2) as starting material and Cl2, ZrCl4 or HfCl4 as transport agents. The lattice constants are a = 6.275(1) Å, c = 19.968(6) Å and Z = 2. Structure determination in the space group P63/mcm (no. 193) let to R1 = 0.032 (wR2 = 0.074). Thorium is surrounded by oxygen like an transbis-capped octahedron (CN = 8) and tantalum like a pentagonal bipyramid (CN = 7).Both coordination polyhedra are for themself arranged to layers (Th to o-, Ta to p-layers) so that in the direction of the c-axes a sequence of layers like p-p-o-p-p-o appears. Therefore the compound is a new representative of the structures described by Jahnberg.
    Notes: Durch chemischen Transport, ausgehend von Gemengen aus ThO2, ZrO2 (bzw. HfO2) und Ta2O5 (1 : 2 : 2) und mit Cl2, ZrCl4 oder HfCl4 als Transportmittel, wurden im Temperaturgefälle 1000°C → 980°C farblose, hexagonale Einkristalle von Th2Ta6O19 mit den Gitterkonstanten a = 6,275(1) Å, c = 19,968(6) Å und Z = 2 erhalten. Die Strukturaufklärung in der Raumgruppe P63/mcm (Nr. 193), die bei R1 = 0,032 (wR2 = 0,074) konvergierte, ergab für Th CN = 8 und Ta CN = 7. Thorium ist in Form eines transbis-bekappten Oktaeders, Tantal pentagonal-bipyramidal von Sauerstoff umgeben.Beide Koordinationspolyeder sind für sich in Schichten (Th in o-, Ta in p-Schicht) so angeordnet, daß sich eine Schichtabfolge p-p-o-p-p-o in c-Richtung ergibt. Demnach ist die Verbindung als neue Variante der von Jahnberg beschriebenen Strukturen anzusehen.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0044-2313
    Keywords: Thia- and selena-arachno-undecaborane ; preparation ; spectroscopy ; ab initio/IGLO ; GIAO/NMR method ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thia- and Selena-arachno-undecaborane 6,7-μ-(CH3E)B10H13. Crystal Structure of arachno-6,7-μ-(CH3Se)B10H13. Theoretical Investigations of the Molecular Structures and 11B NMR Shifts of arachno-6,7-μ-(CH3E)B10H13The reaction of B10H14 with (CH3)2S yields with loss of H2 the base adduct 6,9-[(CH3)2S]2B10H12. Although an analogous reaction between B10H14 with disulfanes or diselenanes was expected to produce 6,9 bridged dichalcogen derivatives, (CH3)2S2 failed to react even under reflux conditions. Trisulfane (CH3)2S3 does react, but the pathway is different and leads to (CH3S)B10H13 2 without loss of H2. Unlike of (CH3)2S2, (CH3)2Se2 yields (CH3Se)B10H13, 3. Both 2 and 3 are formed by substitution of a bridging hydrogen and could be obtained in pure form and characterized 11B NMR spectroscopically. A single crystal X-ray structure analysis also was performed on 3 (space group P21/c). The molecular structures of 2 and 3 were optimized at the MP2 level and 11B NMR shifts were computed at the IGLO-SCF, GIAO-SCF and GIAO-B3LYP levels of theory.
    Notes: Bei der Reaktion zwischen B10H14 und (CH3)2S erfolgt unter H2-Abspaltung eine zweifache Adduktbildung, die zu 6,9-[(CH3)2S]2B10H12 führt. Die analoge Umsetzung zwischen B10H14 mit Disulfanen bzw. Diselenanen führte jedoch nicht zu den 6,9-Dichalkogen-verbrückten Derivaten. Bei der Umsetzung mit (CH3)2S2 findet selbst unter Refluxbedingungen keine Reaktion statt, wohl aber mit dem Trisulfan (CH3)2S3. Die Reaktion verläuft aber nicht unter H2-Abspaltung. Vielmehr wird dabei ein Brücken-H-Atom durch eine CH3S-Gruppe substituiert unter Bildung von (CH3S)B10H13 2. Im Gegensatz zu (CH3)2S2 findet aber mit (CH3)2Se2 ebenfalls eine Brücken-H-Substitution statt, wobei (CH3Se)B10H13 3 gebildet wird. 2 und 3 konnten in reiner Form isoliert und 11B-NMR-spektroskopisch charakterisiert werden. Von 3 wurde eine Röntgenstrukturanalyse durchgeführt (Raumgruppe P21/c) und von 2 und 3 die Molekülstrukturen auf MP2-Niveau optimiert sowie 11B-NMR- Verschiebungen mit IGLO-SCF, GIAO-SCF und GIAO-B3LYP berechnet.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 21 (1888), S. 3135-3136 
    ISSN: 0365-9496
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 21 (1888), S. 3393-3395 
    ISSN: 0365-9496
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 21 (1888), S. 3569-3576 
    ISSN: 0365-9496
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 22 (1889), S. 1-4 
    ISSN: 0365-9496
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 22 (1889), S. 199-201 
    ISSN: 0365-9496
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 22 (1889), S. 301-304 
    ISSN: 0365-9496
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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