ALBERT

All Library Books, journals and Electronic Records Telegrafenberg

X
feed icon rss

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
  • 1
    Electronic Resource
    Electronic Resource
    Ein einfacher Weg zur Herstellung von Alkylpalladium-Verbindungen durch Pd—O-Bindungs-Spaltung in kationischen Bis(ether-phosphan)palladium(II)1-Komplexen mit Grignard-ReagenzienHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1347-1353 
    Details
    ISSN: 0009-2940
    Keywords: Palladium complexes, alkyl-and acyl- ; Ether phosphanes ; Fluxional behavior ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Simple Method for the Preparation of Alkylpalladium Compounds by Pd—O Bond Cleavage in Cationic Bis(etherphosphane)palladium(II) Complexes with Grignard ReagentsHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet.The bis(chelate) complexes [Pd(P∩O)2][ClO4]2 (3a - e) react with methylmagnesium chloride with a concomitant cleavage of two weak Pd—O bonds to give the methyl complexes trans1-ClPd(P∼O)2(CH3) (4a - e) (P ∼ O; η1-P1-coordinated; P∩O: η21-O, P1-chelated; Scheme 1). Diffusion of pentane into the reaction mixture of 4a-e in the presence of the formed magnesium salts yields the cationic complexes trans-[Ch3Pd(P∼O)1-(P∩O)][ClO4] (6a, c). The reaction of 3a-e with benzylmagnesium chloride affords the cationic benzyl complexes cis-[PhCh2Pd(P∼O)(P∩O)][ClO4] (8a-e) in which only one Pd—O bond has been cleaved. In the presence of carbon monoxide 4a-e adn 6a, c are transformed into the corresponding acyl complexes CH3C(O)Pd(P∼O)2Cl (5a-e and [CH3C(O)Pd-(P∼O)(P∩O)][ClO4] (7a, c). Whereas at 183 K variable-temperature 31P{1H}1-NMR measurements of 6a, c, 7a, c indicate a non-rigid behavior of the two differently bound ether-phosphanes, the dynamic process is frozen out for 8a-e. By a lineshape analysis of the spectra the thermodynamic parameters ΔG≢, ΔH≢, and ΔS≢ are obtained. According to a crystal structure analysis 3d and 6c crystallize in the monoclinic space group P21/c with Z=4.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260613
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 2
    Electronic Resource
    Electronic Resource
    Fluktuierendes Verhalten von kationischen cis1-Bis(ether-phosphan)1-palladium(II)1-Komplexen. - 31P-DNMR-spektroskopische Untersuchungen, Linienformanalyse und Bestimmung der thermodynamischen AustauschparameterHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1317-1324 
    Details
    ISSN: 0009-2940
    Keywords: Palladium complexes ; Ether-phosphanes ; NMR, 31P, dynamic, line-shape analysis ; Fluxional behavior ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluxional Behavior of Cationic cis Bis(ether-phosphane)palladium(II) Complexes. - 31P-DNMR Spectroscopic Investigations, Line-Shape Analysis, and Determination of Rearrangement BarriersHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet.Reaction of X2Pd(P∼O)2 (X=Cl: 1a - g, k - n, p; X=Br: 1′; X=I: k″, l″, o″) with stoichiometric amounts of AgClO4 results in the formation of the monochelate complexes cis-[ClPd(P∼O)(P∩O)][ClO4] (2a - g, k - n, p, l′, l″) (P∼O: η11-P-coordinated; P∩O: η21-O,P-chelated). In the case of compounds 1o, 1k″, and 1o″, which are provided with less basic etherphosphanes, the halide-bridged dimers [(μ1-X)Pd(P∼O)2]2[ClO4]2 (3o, k″, o″) are obtained. Temperature-dependent 31P{1H}1-NMR spectra of the fluxional complexes 2a - g, k - n, p, l′, l″ lead to δG≢ values. By using a modified version of DNMR5, computer-generated spectra of 2a, b, f, k, l, p, l′, l″ were obtained and fitted to the experimental spectra. Graphic application of the Eyring equation to the kinetic data afforded the thermodynamic parameters δH≢, δS≢, and δG≢. The δS≢ values are in agreement with an associative exchange mechanism for 2a, b, f, l, p, l′, l″ and with a dissociative exchange mechanism for 2k, 2k and 3o crystallize in the monoclinic and triclinic space group P21/c and P&1marc; with Z=4 and Z=2, respectively.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260608
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...