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  • 1980-1984  (6)
  • 1975-1979
  • 1982  (6)
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  • 1980-1984  (6)
  • 1975-1979
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 2181-2191 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation, Structure, and Thermal Behaviour of (2-Chloroacyl)diphenylphosphanes - a New Pathway to ChloroketenesThe chlorinated acylphosphanes RC(O)—PPh2 (2a-f) are obtained by the reaction of the acyl chlorides RC(O)Cl (1a-f) with (CH3)3SiPPh2 in ether at -80°C. HCCl2C(O)—PPh2 (2c) crystallizes monoclinicly in the space group P21/c with Z = 8. As a result of steric caused electronic effects with increasing degree of chlorination in the series 2b → 2c → 2d a stepwise high field shift of the signals in the 31P{1H}-NMR spectra is observed. 2b-d,f are thermally labile and decompose with formation of ClPPh2 (3) and ketene at 80°C. The chloroketenes HCClCO (4) and CH3CClCO (5) are detected for the first time directly by means of their 13C NMR spectra. Between 0 and 40°C 2d also yields Cl3PPh2 (6). With cyclohexene or aniline 4 reacts to give the trapping products 8 and 9, respectively.
    Notes: Die chlorierten Acylphosphane RC(O)—PPh2 (2a-f) erhält man bei -80°C durch Umsetzung der Säurechloride RC(O)Cl (1a-f) mit (CH3)3SiPPh2 in Ether. HCCl2C(O)—PPh2 (2c) kristallisiert monoklin in der Raumgruppe P21/c mit Z = 8. Infolge sterisch bedingter elektronischer Effekte beobachtet man mit zunehmendem Chlorierungsgrad in der Reihe 2b ° 2c → 2d eine schrittweise Hochfeldverschiebung der Signale in den 31P{1H}-NMR-Spektren. 2b-d,f sind thermisch labil und zerfallen bei 80°C unter Bildung von ClPPh2 (3) und Keten. Die Chlorketene HCClCO (4) und CH3CClCO (5) konnten erstmals direkt durch ihre 13C-NMR-Spektren nachgewiesen werden. Zwischen 0 und 40°C liefert 2d auch Cl3PPh2 (6). Mit Cyclohexen oder Anilin reagiert 4 zu den Abfangprodukten 8 bzw. 9.
    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 115 (1982), S. 2478-2486 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Thermal Behaviour, and Stabilization of (3-Chloroacyl)- and (4-Chloroacyl)diphenylphosphanesThe propionyl- and butyryldiphenylphosphanes RC(O)-PPh2 (2a-c) [R = ClCH2CH2 (a), CH3CHClCH2 (b), ClCH2[CH2]2 (c)] are obtained by the reaction of the acyl chlorides 1a-c with (CH3)3Si-PPh2 at -40°C in ether. 2a, b are thermally labile and polymerize under elimination of HCl. The formation of ketenes is not observed. By the reaction with BrMn(CO)5 2a, b were stabilized as complexes (OC)4BrMnPPh2C(O)R (3a, b) and compared with 3d, e [R = CH3CHCl (d), F2CCl (e)]. On the basis of an X-ray crystallographic investigation 3b crystallizes monoclinicly in the space group P21/c with Z = 4.
    Notes: Die Propionyl- und Butyryldiphenylphosphane RC(O)-PPh2 (2a-c) [R = ClCH2CH2 (a), CH3CHClCH2 (b), ClCH2[CH2]2 (c)] erhält man durch Einwirkung der Säurechloride 1a-c auf (CH3)3Si—PPh2 bei -40°C in Ether. 2a,b sind thermisch labil und polymerisieren unter HCl-Eliminierung. Ketenbildung wird nicht beobachtet. Durch Umsetzung mit BrMn(CO)5 wurden 2a, b in Form der Komplexe (OC)4BrMnPPh2C(O)R (3a, b) stabilisiert und mit 3d, e [R = CH3CHCl (d), F2CCl (e)] verglichen. Aufgrund einer Röntgenstrukturanalyse kristallisiert 3b monoklin in der Raumgruppe P21/c mit Z = 4.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, VIII. Sulfur Dioxide and Carbon Monoxide Insertion Reactions into the Metal-Carbon σ-Bond of MetallacycloalkanesThe manganacyclohexane derivative (1a) is obtained by nucleophilic elimination-cycloaddition from (F3CSO2OCH2)2C(CH3)2 and Na2[(OC)4MnP(CH3)2O] in DME. At -40°C the analogous compounds (1a′, 1b′) [M = Mn (a′), Re (b′)] take up SO2 and change into the cyclic sulfinato-S complexes (2a′, 2b′). 1a′, 2b′ give triclinic crystals which belong to the space group P1 with Z = 2 and 4, respectively. The AlBr3 supported CO insertion into the Re—C σ-bond of 1b′ results in the formation of the cyclic ketone (4b′) via the adduct (3b′).
    Notes: Das Manganacyclohexan-Derivat (1a) erhält man durch nucleophile Eliminierungscycloaddition aus (F3CSO2OCH2)2C(CH3)2 und Na2[(OC)4MnP(CH3)2O] in DME. Bei -40°C nehmen die analogen Verbindungen (1a, 1b′) [M = Mn (a′), Re (b′)] SO2 auf und gehen in die cyclischen Sulfinato-S-Komplexe (2a′, 2b′) über. 1a′, 2b′ kristallisieren triklin in der Raumgruppe P1 mit Z = 2 bzw. 4. Die AlBr3-unterstützte CO-Insertion in die Re-C-σ-Bindung von 1b′ führt über das Addukt (3b′) zum cyclischen Keton (4b′).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract.Das vollständige Manuskript dieser Zuschrift erscheint in: Angew. Chem. Suppl. 1982, 893-906
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 21 (1982), S. 913-921 
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 21 (1982), S. 355-356 
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract.The complete manuscript of this communication appears in: Angew. Chem. Suppl. 1982, 913. DOI:10.1002/anie.198209130
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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