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  • 1
    Electronic Resource
    Electronic Resource
    Synthese, Kristallstruktur und fluktuierendes Verhalten von cis-Cl2Ru(CO)(P∽O)(P^O) mit cis-ständigen (Ether-Phosphan)-LigandenHerrn Professor Wolfgang Beck zum 60. Geburtstag gewidmet. (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1363-1367 
    Details
    ISSN: 0009-2940
    Keywords: Ruthenium(II) complexes ; Ether phosphanes ; Fluxional behavior ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis, Crystal Structure, and Fluxional Behavior of cis-Cl2Ru(CO)(P∽O)(P^O) with cis-Positioned (Ether-Phosphane) LigandsReaction of the ether-phosphane ligands 2a-c with Cl2Ru-(PPh3)3 (1) results in the formation of the bis(chelate) complexes trans-Cl2Ru(P^O)2 (3a-c) (P∽O = η1-P-coordinated; Pb̂O = η2-O,P-coordinated). With CO both Ru-O bonds are cleaved to give all-trans-Cl2Ru(CO)2(P∽O)2 (4a-c). The mono(chelate) complexes 5a-c are obtained from stoichiometric amounts of 3a-c and 4a-c. Upon heating the kinetically controlled products 5a-c are transformed into the thermodynamically more stable isomers cis-Cl2Ru(CO)(P∽O)(P^O) (6a-c). Both 5a-c and 6a-c show fluxional behavior. The higher coalescence temperatures and estimated ΔG≠ values of 6a-c (75, 67, and 70°C, respectively) compared to 5a-c (55, 0, and -10°C, respectively) indicate different exchange mechanisms for 5 and 6. According to an X-ray structure analysis, 6b crystallizes in the monoclinic space group P21/c with Z = 4. The action of CO on 6a-c affords the cis,cis,trans complexes 7a-c.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250609
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  • 2
    Electronic Resource
    Electronic Resource
    Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XXXVIII. Synthese, Eigenschaften und fluktuierendes Verhalten von (Ether-Phosphan)palladium-Komplexen (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 2255-2260 
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    ISSN: 0009-2940
    Keywords: Ether-phosphines ; Palladium complexes ; Fluxional behavior ; Hydrogenation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel Basic Ligands for the Homogeneous Catalytic Carbonylation of Methanol, XXVIII.  -  Synthesis, Properties and Fluxional Behavior of (Ether-Phosphine)palladium ComplexesCl2Pd(COD) (1) (COD = 1,5-cyclooctadiene) reacts with 1 equiv, of the (ether-phosphine) ligand Ph2P∼D (2a-c) (D = CH2C4H7O (a), CH2C4H7O2 (b), CH2CH2OCH3 (c)] to give the dimeric complexes [μ-ClPdCl(Ph2P∼D)]2 (3a-c) (P∼D = η1-P-coordinated). According to the field-desorption mass spectra which show only one peak for the monomeric moieties ClPd(Ph2P∼D), 3a-c have a very weak Pd2Cl2 bridge. trans-Cl2Pd(Ph2P∼D)2 (4a-c) is obtained either from 3a-c and 2a-c by cleaving the Pd2Cl2 bridge or from 1 and 2 equiv. of the ligands 2a-c. 4c crystallizes in the monoclinic space group P21/c with Z = 2. AgClO4 selectively abstracts one Cl⊖ ligand from 4a-c which results in the formation of the cationic complexes [trans-(Ph2P∩D)(Ph2P∼D)PdCl]⊕ (5a-c) (P∩D = η2-D,P-coordinated) containing one chelated and one η11-P-bonded (ether-phosphine) ligand. 5a-c show fluxional behavior which is demonstrated by temperature-dependent 31P{1H}-NMR investigations. The coalescence points have been determined and are at 253 (5a), 303 (5b), and 283 K (5c). The activation enthalpies ΔG
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901231205
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  • 3
    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
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  • 4
    Electronic Resource
    Electronic Resource
    Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XXVI. Dynamisches und reaktives Verhalten von (Ether-Phosphan)ruthenium(II)-Komplexen in Abhängigkeit von der O-Basizität (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1469-1474 
    Details
    ISSN: 0009-2940
    Keywords: Ruthenium complexes ; Ether-phosphines ; O-Basicity ; Fluxional behavior ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel Basic Ligands for the Homogeneous Catalytic Carbonylation of Methanol, XXVIl). - Dynamic and Reactive Behaviour of (Ether-Phosphane)Ruthenium(II) Complexes in Dependence on the o-BasicityReaction of the ether-phosphane ligand Ph2PCH2C4H7O2 (3a) with Cl2Ru(PPh3)3 (2) results in the formation of the bis(chelate) complex trans-Cl2Ru(P^O)2 (4a). (P∼O = η1—P-coordinated; P^O = η2—O,P-coordinated). With CO both Ru-O bonds are cleaved to give all-trans-Cl2Ru(CO)2(P∼O)2 (7a). At 35°C 7a is transformed into the monocarbonyl ruthenium complex trans-Cl2(P^O)(P∼O)RuCO (5a) with elimination of one CO molecule. On heating all-trans-7a to 110°C in toluene the thermodynamically more stable complex cis-Cl2(OC)2Ru(trans-P∼O)2 (6a) is obtained. All reaction steps are reversible. Upon irradiation cis,cis,trans-6a is retransformed at 40°C into 4a via all-trans-7a and 5a. The latter and the corresponding complexes 5b, c, containing THF and CH2OCH3 as ether substituents, show fluxional behaviour. The coalescence temperatures (10, 80, and 55°C, resp.) and the estimated ΔG≢ values (52, 65, and 59 kJ/mol, resp.) of the exchange process indicate the weakest Ru-O contact in 5a compared to 5b, c. The lower basicity of the dioxanyl function is also responsible for the different reaction behaviour of 4a, 5a, and 7a compared to the corresponding complexes with the ligands 3b, c.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230704
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  • 5
    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
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