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  • 1990-1994  (3)
  • 1,2,3-Diazaphospholes  (1)
  • 1-Metalla-1,3,5-trienes of tungsten, cyclization to cyclopentadiene complexes  (1)
  • Aluminum sulfide  (1)
  • 1
    ISSN: 0009-2940
    Keywords: Cyclopentadienes, synthesis of ; [3 + 2] Cycloadditions of 1-metalla-1,3-dienes and alkynes ; 1-Metalla-1,3,5-trienes of tungsten, cyclization to cyclopentadiene complexes ; η1-Cyclopentadiene tungsten complexes ; Aminocarbene complexes of chromium and tungsten ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Syntheses via Transition Metal Complexes, 54.  -  Cyclopentadienes from 1-Metalla-1,3-dienes and Alkynes by Cyclization of Intermediate 1-Metalla-1,3,5-trienes (Metal = Tungsten)We report on first examples of the formation of cyclopentadienes from a 1-metalla-1,3-diene LnM=C-C=C [LnM = W(CO)5] and an alkyne in [3 + 2] cycloaddition multistep reactions. In a first step the alkyne Et2N-C=C-Me (2) adds to the 1-metalla-1,3-diene (CO)5W = C(OEt)-CH=CHPh (1b) to give 1-metalla-1,3,5-trienes (CO)5W=C(NEt2)-CMe=C(OEt)-CH=CHPh (3b) and (CO)5W=C(OEt)-CH=C(NEt2)-CMe=CHPh (4b). In a second step 3b cyclizes to thecyclopentadiene complex 5, which has an η1 ylide-type structure as established by an X-ray analysis. Hydrolysis of 5 leads to the formation of a 3-aminocyclopentenone 7. The 1-metalla-1,3,5-triene 4b yields a cyclopentadiene complex 8. In contrast to 5 the carbon skeleton of 8 has a connectivity different from that of the C3 unit of the 1-metalla-1,3-diene 1.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 411-414 
    ISSN: 0009-2940
    Keywords: Phosphaalkyne, amino- ; [3 + 2] Cycloaddition ; 1,2,4-Diazaphospholes ; 1,2,3-Diazaphospholes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactive E = C(p - p)π Systems, XXXII[1].  -  First Representatives of Amino-Substituted 1,2,4-Diazaphospholes(Diisopropylamino)phosphaethyne iPr2N - C≡P reacts at 20° C in a [3 + 2] cycloaddition with (trifluoromethyl)diazomethane (2a) or methyl diazoacetate (2b) to yield a mixture of the corresponding regioisomers 1H-1,2,4-diazaphospholes (5a or 5b) and 1H-1,2,3-diazaphospholes (6a or 6b) in quantitative yields (isomer ratio: 5a/6a = 2:1; 5b/6b = 4:1). X-ray diffraction studies on 5a and 5b indicate a delicate charge balance in the bonding system of 1H-1,2,4,σ2-diazaphospholes under the influence of the exocyclic push/pull substituents iPr2N and CF3 or CO2Me, respectively.
    Additional Material: 2 Ill.
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  • 3
    ISSN: 0044-2313
    Keywords: Aluminum sulfide ; crystal structure ; chemical transport ; five-coordinated aluminum ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of a Novel Hexagonal Modification of Al2S3 with Five-coordinated AluminumA new hexagonal high temperature modification of Al2S3 could be prepared by chemical vapour transport with iodine (860 → 750°C) or by annealing of α -Al2S3 at 550°C. According to the single crystal X-ray structure determination the novel form of Al2S3 crystallizes in space group P 61 (No. 169) with a = 6.491(1), c = 17.169(4) Å, V = 626.5 Å3, Z = 6; R = 0.0253. In this modification one half of the aluminum atoms are tetrahedrally coordinated [d(Al—S): 2.226-2.267 Å], whereas the other half are in trigonal bipyramidal coordination of five S atoms with bond lengths of 2.272-2.315 Å (equatorial) and 2.495-2.521 Å (axial).Aluminum in AlS5 coordination is observed for the first time in this compound. The crystal structure is isotypic to In2Se3 and AlInS3. In addition, results of a refinement of the α -Al2S3 crystal structure are reported which were obtained on crystals prepared also by chemical vapour transport with iodine.
    Notes: Eine bisher noch nicht beschriebene hexagonale Hochtemperatur-Modifikation von Al2S3 konnte in reiner Form entweder durch chemischen Transport mit Iod (860 → 750°C) oder durch Tempern von α -Al2S3 oberhalb 550°C erhalten und durch eine Einkristall-Röntgenstrukturanalyse charakterisiert werden.Die neue Form des Al2S3 kristallisiert in der Raumgruppe P 61 (Nr. 169) mit a = 6,491(1), c = 17,169(4) Å, V = 626,5 Å3, Z = 6; R = 0,0253. In dieser Modifikation liegt die eine Hälfte der Aluminiumatome tetraedrisch koordiniert vor [d(Al—S): 2,226-2,267 Å], während die andere Hälfte trigonal-bipyramidal von fünf S-Atomen mit Al—S-Bindungslängen von 2,272 bis 2,315 Å (äquatorial) und 2,495-2,521 Å (axial) umgeben ist.Aluminium in AlS5-Koordination ist bisher unbekannt und wird hier zum ersten Mal beobachtet. Die Struktur ist isotyp zu In2Se3 und AlInS3. Zusätzlich wird über die Verfeinerung der Kristallstruktur α von -Al2S3 an Einkristallen berichtet, die ebenfalls durch chemischen Transport mit Iod hergestellt wurden.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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