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  • 1975-1979  (3)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1128-1139 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbyne Complexes, IX: Reaction of Pentacarbonyl(hydroxyorganylcarbene)tungsten Complexes with Dicyclohexylcarbodiimide (DCCD) to Form Binuclear Carbene Carbyne ComplexesPentacarbonyl(hydroxyorganylcarbene)tungsten complexes react with dicyclohexylcarbodiimide (DCCD) to yield the binuclear carbene carbyne complexes 2a-d and 3 by intermolecular elimination of water and substitution of the trans-Co-ligand by an acylpentacarbonylmetallate group. The constitution of the carbene carbyne complexes is elucidated by their i. r., 1H n. m. r., and 13C. n. m. r. spectra and reactions with tetraalkylammonium halides, which produce trans-tetracarbonylhalogeno(organylcarbyne)tungsten complexes and tetraalkylammonium acylpentacarbonylmetallates.
    Notes: Pentacarbonyl(hydroxyorganylcarben)wolfram-Komplexe reagieren mit Dicyclohexylcarbodiimid (DCCD) unter intermolekularer Wasserabspaltung und Substitution des trans-ständigen CO Liganden durch einen Acylpentacarbonylmetallat-Rest zu zweikernigen Carben-Carbin-Komplexen 2a-d) und 3. Die Konstitutionsaufklärung der Carben-Carbin-Komplexe gelingt durch ihre IR-,1H-NMR-und 13C-NMR-Spektren, sowie durch ihre Reaktion mit Tetraalkylammonium halogeniden, die zu trans-Tetracarbonylhalogeno(organylcarbin)wolfram-Komplexen und Tetraalkylammonium-acylpentacarbonylmetallaten führt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1120-1127 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition metal Carbene Complexes, LXXXIII: Synthesis and Reactions of Binuclear Hydroxycarbene Anhydride Chromium Complexes[Pentacarbonyl(hydroxyphenylcarbene)chromium]anhydride(1) reacts with dimethylamine to give pentacarbonyl[(dimethylamino)phenylcarbene]chromium(0) (2) and dimethylammoniumbenzoylpentacarbonylchromate (3). The acidic, p-phenyl-substituted (arylhydroxycarbene)pentacarbonyl chromium complexes (4,5) yield with dicyclohexylcarbodiimide (DCCD) by intermolecular water elimination binuclear (arylhydroxycarbene) pentacarbonylchromium anhydride complexes (6,7). The reaction of the anhydride complexes with tetraalkylammoniumhalides to give trans-(arylcarbyne) tetracarbonylhalogenochromium complexes and tetraalkylammoniumacylpentacarbonylchromates shows a strong in fluence of phenyl-substituents on the reactivity of the anhydride complexes.
    Notes: [Pentacarbonyl(hydroxyphenylcarben)chrom]-anhydrid (1) reagiert met Dimethylamin zu Pentacarbonyl[(dimethylamino)phenylcarben]chrom(0) (2) und Dimethylammonium-benzoylpentacarbonylchromat (3). Die aciden p-phenyl-substituierten (Arylhydroxycarben)pentacarbonylchrom-Komplexe (4,5) ergeben mit Dicyclohexylcarbodiimid (DCCD) unter intermolekularer Wasserabspaltung die zweikernigen [(Arylhydroxycarben) pentacarbonylchrom]-anhydrid-Komplexe (6,7). Die Umsetzung der Anhydridkomplexe mit Tetraalkylammonium-halogeniden, die zu trans-(Arylcarbin)tetracarbonylhalogenochrom-Komplexen und Tetraalkylammonium-acylpentacarbonylchromaten führt, zeigt einen starken Einfluß der Phenylsubstituenten auf die Reaktivität der Anhydridkomplexe.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1868-1886 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXXXV. Pentacarbonyl (organylcarbene)chromium and-tungsten as Amino-Protecting Groups in Peptide SynthesesPentacarbonyl(methoxyorganylcarbene) complexes of chromium and tungsten (organyl = CH3, C6H5) react with amino acid esters to give aminocarbene complexes, in which the pentacarbonyl (organylcarbenyl) groups act as amino-protecting groups (1-15. The alkaline hydrolysis of the esters yields derivatives with free carboxyl groups (16-18), at which peptide coupling reactions are carried out by means of the dicyclohexylcarbodiimide /N-hydroxysuccinimide (DCCD/HOSU) method. The carbene complex protective groups can be cleaved off with trifluoroacetic acid (TFE) In the case of pentacarbonyl (organylcarbenyl) tungsten groups side reactions are observed. The cleavage of the carbene complex protecting group may also be achieved with 80% acetic acid. The pentacarbonyl(phenylcarbenyl) tungsten group of Wpc-Gly-OMe (8) can be cleaved off by BBr3 at - 25°C.
    Notes: Pentacarbonyl(methoxyorganylcarben)-Komplexe des Chroms und Wolframs (Organyl = CH3, C6H5) reagieren mit Aminosäureestern zu Aminocarben-Komplexen, in denen die Pentacarbonyl-(organylcarbenyl)-Reste als Amino-Schutzgruppen wirken (1-15). Die alkalische Verseifung der Ester liefert Derivate mit freier Carboxylgruppe (16-18), an denen Peptidverknüpfungen mit Hilfe der Dicyclohexylcarbodiimid/N-Hydroxysuccinimid (DCCD/HOSU)-Methode durchgeführt werden. Die Carbenkomplex-Schutzgruppen können mit Trifluoressigsäure (TFE) wieder abgespalten werden. Dabei beobachtet man bei Pentacarbonyl(organylcarbenyl)wolfram-Gruppen Nebenreaktionen. Die Abspaltung der Carbenkomplex-Schutzgruppe gelingt auch mit 80proz. Essigsäure. Die Pentacarbonyl(phenylcarbenyl)wolfram-Gruppe von Wpc-Gly-O Me (8) läßt sich mit BBr3 bei - 25°C abspalten.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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