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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 608 (1992), S. 33-42 
    ISSN: 0044-2313
    Keywords: Diacylphosphines ; Di-cyclohexoylposphine ; Diadamant-1-oylphosphine ; keto-enol tautomerism ; NMR-parameters, thermodynamic data ; X-ray structure determination ; very short O‥H‥O bridge ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Acyl- and Alkylidenephosphines. XXXII. Di-cyclohexoyl- and Diadamant-1-oylphosphine - Keto-Enol Tautomerism and StructureLithium dihydrogenphosphide · DME (1) [12] and cyclo-hexoyl or adamant-1-oyl chloride react in a molar ratio of 3:2 to give lithium di-cyclo-hexoylphosphide · DME and the corresponding diadamant-1-oylphosphide.2THF (1) resp. Treatment of these two compounds with 85% tetrafluoroboric acid. diethylether adduct yields di-cyclo-hexoyl- (1b) and diadamant-1-oylphosphine (1c). In nmr spectroscopic studies 1b over a range of 203 to 343 K, a strong temperature dependence of the keto-enol equilibrium is found; thermodynamic data characteristic for the formation of the enol tautomer (ΔH0 = -4.3 kJ. mol-1; ΔS0 = -9.2 J. mol-1. K (-1) are compared of 1,3-diketones.The enol tautomer of diadamant-1-oylphosphine (E-1c) as obtained from a benzene solution in thin colourless plates, crystallizes in the monoclinic space group P21/c {a = 722.2(2); b = 1085.5(4); c = 2434.8(5) pm; ß = 96.43(2)° at -100 ± 3°C; Z = 4}. An X- ray structure analysis (Rw = 0.033) shows bond lengths and angles to be almost identical within the enolic system (P—C 179/180; C—O 130/129; C—C(adamant-1-yl) 152/153 pm; C—P—C 99°; P—C—O 124°/124°; P—C—C 120°/120°; C—C—O 116°/116°. The geometry of the very strong, but probably asymmetric O‥H‥O bridge is discussed (O—H 120/130, O‥O 245 pm).
    Notes: Aus Lithium-dihydrogenphosphid · DME (1) [12] und cyclo-Hexoyl- bzw. Adamant-1-oyl-chlorid im Molverhältnis 3:2 zugängliches Lithium-di-cyclo-hexoylphosphid · DME und -diadamant-1-oylphosphid · 2THF 1) reagieren mit 85proz. Tetrafluoroborsäure · Diethylether-Addukt zu Di-cyclo-hexoyl- 1b) und Diadamant-1-oylphosphan (1 c). Die Lage des Keto-Enol-Gleichgewichts zwischen 203 und 343 K sowie thermodynamische Daten zur Bildung des Enol-Isomers ΔH0= -4,3kJ.Mol-1; ΔS0;=-9,2 J · mol-1 · K-1 () wurden NMR-spektroskopisch an einer 2 M Lösung des bei +20°C flüssigen Di-cyclo-Hexoyl-Derivates 1b in d8-Toluol ermittelt und mit Werten von 1,3-Diketonen verglichen.Das farblose, sich aus Benzol in dünnen Plättchen abscheidende Enol-Tautomer des Diadamant-1-oylphosphans (E-1 c) kristallisiert monoklin in der Raumgruppe P21/c {a = 722,2(2) b = 1085,5(4); c = 2434,8(5) pm; ß = 96,43(2)° bei - 100 ± 3°C; Z = 4}. Nach den Ergebnissen der Röntgenstrukturanalyse (Rw=0,033) weist das Molekül in beiden des Hälften des Enolrings nahezu identische Bindungslängen und -winkel auf P—C 179/180; C—O 130/129; C—C(Adamant-1-yl) 152/153 pm; C—P—C 99°; P—C—O 124°/124°; P—C—C 120°/120°; C—C—O 116°/116°. Die Geometrie der sehr starken, aber vermutlich asymmetrischen O‥H‥O-Brücke wird diskutiert (O—H 120/130; O‥O 245 pm).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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