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  • Ether phosphanes  (4)
  • Ether-phosphanes  (4)
  • 1
    Digitale Medien
    Digitale Medien
    η1-P- und η2-OP-gebundene (Ether-phosphan)osmium(II)-Komplexe und ihre gegenseitige Umwandlung (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 541-550 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Ether phosphanes ; Osmium(II) complexes ; Conversion ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: η1-P- and η2-OP-Bonded (Ether-Phosphane)Osmium(II) Complexes and their Mutual ConversionReactions of cis-Br2Os(CO)4 with the (ether-phosphane) ligands 2a-f results in the formation of the cis,cis,trans-complexes Br2Os(CO)2(P ∼ O)2 (3a-f). 3b crystallizes in the mono-clinic space group P21/c with Z = 4. Irradiation of 3a-f leads to the cleavage of a further CO group and the formation of an Os—O bond to give the mono(chelate) complexes Br2Os(CO)-(PO) PO (5a-f), with one of the O,P ligands being bidentate. 5a-f exist as mixtures of different trans-P (A,B) and cis-P isomers (C-G). Dependent on the fact that a reversible cis/trans equilibrium or an irreversible trans → cis transformation is possible or that no trans-P isomers are present at any temperature, 5a-f may be classified in three categories. Inter-conversion of the isomers A-G results from dissociation of the η1-P coordinated ether-phosphane and concomitant occurrence of the 16e- species Br2Os(CO)(PO) (8). From temperature-dependent 31P{1H}-NMR spectroscopic investigations the temperature for the reversible opening of the metal-oxygen contact is determined. The reversible opening leads to the complexes Br2Os(CO)(PO)2 (9) with a vacant coordination site depending on the Os-O bonding strength. 5a-f react with CO to give all-trans-Br2Os(CO)2(PO)2 (4a-f). The action of the ether-phosphanes 2a-f on OsBr2(PPh3)4 (7) affords the bis(chelate) complexes Br2Os(PO)2 (6a-f) which add carbon monoxide to form all-trans-4a-f.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19921250303
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  • 2
    Digitale Medien
    Digitale Medien
    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
    Schlagwort(e): Palladium complexes, alkyl-and acyl- ; Ether phosphanes ; Fluxional behavior ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19931260613
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  • 3
    Digitale Medien
    Digitale Medien
    Control of the SO2 Coordination Mode at the (Monochelate)rhodium Complex ClRh(P∼O) with the Hemilabile Ligand Cy2PCH2CH2OCH3Dedicated to Professor Michael Hanack on the occasion of his 65th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1103-1105 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Sulfur dioxide ; Rhodium complexes ; Ether-phosphanes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The SO2 coordination mode at the rhodium complex [ClRh(P∼O)()] (1) [ = η2(O,P)-chelated Cy2PCH2CH2OCH3 ligand; P∼O = =1(P)-coordinated] is controlled by the hemilabile ligand Cy2PCH2CH2OCH3 and shows a dependence on the polarity of the solvent. In polar organic solvents (e.g. acetone) the addition of sulfur dioxide results in the formation of a trigonal-pyramidal oriented SO2 group in [ClRh(η1-SO2)(P∼O)()] (2a). However, in nonpolar media (e.g. n-hexane) a trigonal-coplanar geometry of the SO2 unit in [ClRh(η1-SO2)(P∼O)2] (2b) is favored.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19961290920
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  • 4
    Digitale Medien
    Digitale Medien
    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
    Schlagwort(e): Ruthenium(II) complexes ; Ether phosphanes ; Fluxional behavior ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19921250609
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  • 5
    Digitale Medien
    Digitale Medien
    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
    Schlagwort(e): Palladium complexes ; Ether-phosphanes ; NMR, 31P, dynamic, line-shape analysis ; Fluxional behavior ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19931260608
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  • 6
    Digitale Medien
    Digitale Medien
    Trägerfixierte Organometallkomplexe, III. Polysiloxan-gebundene (Ether-phosphan)ruthenium(II)-Komplexe und ihre CP-MAS-NMR-spektroskopische CharakterisierungHerrn Professor Wolfgang Beck zum 60. Geburtstag gewidmet. (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 2385-2390 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Ether-phosphanes ; Ruthenium complexes ; Polysiloxane matrices ; CP-MAS NMR ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Carrier-Bound Organometallic Complexes, III[1]. - Polysiloxane-Bound (Ether-phosphane)ruthenium(II) Complexes and Their CP-MAS NMR-Spectroscopic CharacterizationThe reaction of the functionalized ether-phosphane ligand CH3O(CH2)2P(Ph)(CH2)3Si(OMe)3 (1c) with Cl2Ru(PPh3)3 (2) and HRuCl(CO)(PPh3)3 (3) results in the formation of the mono-chelated (ether-phosphane)ruthenium(II) complex Cl2Ru(P∼O)2(P∼O) (4c) and the hydride HRuCl(CO)(P∼O)3 (5c) (P∼O: η1-P-coordinated; P∼O: η2-O∼P-coordinated). Compounds 4c and 5c are polycondensated to the corresponding polysiloxane-bound complexes 4c′ and 5c′. 31P-chemical shifts of the immobilized species 4c′ and 5c′ in the solid-state CP-MAS NMR spectra are compared with those of the 31P{1H}-NMR spectra of monomeric complexes 4b, c and 5b, c with the ligands CH3O(CH2)2P(Ph)(CH2)3SiMe3 (1b) and 1c in solution. No change in the structure between the monomeric and polymeric species could be observed. According to 29Si CP-MAS NMR-spectroscopic investigations the polysiloxane chains are connected by ruthenium complexes to a network with favourable properties. The chelated polysiloxane-bound red complex 4c′ adds CO in the solid state to give quantitatively yellow all-trans-Cl2Ru(CO)2(P∼O)2 (6c′). In the presence of carbon monoxide there is an equilibrium between 5c′ and HRuCl(CO)2(P∼O)2 (7c′) which was also found in solution for 5b, c and 7b, c. The reactions indicate that the chemistry of polysiloxane-bound ether-phosphane complexes can well be compared with the chemistry in solution. 31P CP-MAS NMR spectra of the complexes 4c′ and 5c′ are strongly dominated by a chemical shift anisotropy which shows a fingerprint pattern both for monomeric crystalline complexes 4a, 5a [containing ligand Ph2P(CH2)2OCH3 (1a)] and polysiloxane-bound phosphane complexes 4c′ and 5c′.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19921251110
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  • 7
    Digitale Medien
    Digitale Medien
    (Ether-phosphan)eisen(II)1-Komplexe mit den Koordinationszahlen Vier, Fünf und Sechs (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 889-893 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Iron(II) complexes ; Ether phosphanes ; Coordination numbers ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: (Ether-phosphane)iron(II) Complexes with the Coordination Numbers Four, Five, and SixPhotolysis of cis,cis,trans1-Br2(OC)2 Fe(P∑O)2 (1a, b) [O,P=Ph2PCH2CH2OCH3 (a), Ph2PCH2C4H7O (b)] results in the formation of the iron(II) complexes Br2Fe(P∼O)2 (2a), [BrFe-(P∩O)(μ1-Br)]2 (4b), and [trans1-Br2Fe(P∩O)(μ1-CO)]2 (5a) with the coordination numbers four, five, and six, respectively. 2a crystallizes in the triclinic space group P\documentclass{article}\pagestyle{empty}\begin{document}$\bar{1}$\end{document} with Z=2 and has two monodentated O,P functions (P∼O: η1-P1-coordinated; P∩O:η2-O,P1-coordinated). The dimeric complex 4b with two O∩P-chelated ligands crystallizes in the orthorhombic space group Pbca with Z=4. 2a and 4b, which react under CO pressure to give the starting complexes 1a, b, are also accessible from the ether-phosphanes 3a, b and anhydrous FeBr2.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19931260406
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  • 8
    Digitale Medien
    Digitale Medien
    Trägerfixierte Organometallkomplexe. VI. Charakterisierung und Reaktivität Polysiloxan-gebundener (Ether-phosphan)ruthenium(II)-KomplexeProfessor Wilhelm Preetz zum 60. Geburtstage gewidmet (1994)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 1142-1150 
    Details
    ISSN: 0044-2313
    Schlagwort(e): Ether-phosphanes ; ruthenium complexes ; polysiloxane-matrices ; heteronuclear CP-MAS NMR spectroscopy, Chemical Shift Anisotropy (CSA) ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Supported Organometallic Complexes. VI. Characterization und Reactivity of Polysiloxane-Bound (Ether-phosphane)ruthenium(II) ComplexesThe ligands PhP(R)CH2D [R = (CH3O)3Si(CH2)3; D = CH2OCH3 (1b); D = tetrahydrofuryl (1c); D = 1,4-dioxanyl (1d)] have been used to synthesize (ether-phosphane)ruthenium(II) complexes, which have been copolymerized with Si(OEt)4 to yield polysiloxane-bound complexes. The monomers cis,cis,trans-Cl2Ru(CO)2(P ∼ O)2 (3b) and HRuCl(CO)(P ∼ O)3 (5b) were treated with NaBH4 to form cis,cis,trans-H2Ru(CO)2(P ∼ O)2 (4b) and H2Ru(CO)(P ∼ O)3 (6b), respectively (P ∼ O = η1-P coordinated; = η2- coordinated). Addition of Si(OEt)4 and water leads to a base catalyzed hydrolysis of the silicon alkoxy-functions and a precipitation of the immobilized counterparts 4b′, 6b′. The polysiloxane matrix resulting by this new sol gel route has been described under quantitative aspects by 29Si CP-MAS NMR spectroscopy. 4b′ reacts with carbon monoxide to form Ru(CO)3(P ∼ O)2 (7b′). Chelated polysiloxane-bound complexes Cl2Ru()2 (9c′, d′) and Cl2Ru()(P ∼ O)2 (10b′, c′) have been synthesized by the reaction of 1b-c with Cl2Ru(PPh3)3 (8) followed by a copolymerization with Si(OEt)4. The polysiloxane-bound complexes 9c′, d′ and 10b′, c′ react with one equivalent of CO to give Cl2Ru(CO)()(P ∼ O) (12b′-d′). Excess CO leads to the all-trans-complexes Cl2Ru(CO)2(P ∼ O)2 (14b′-d′), which are thermally isomerized to cis,cis,trans-3b′-d′. The chemical shift anisotropy of 31P in crystalline Cl2Ru()2 (9a, R = Ph, D = CH2OCH3) has been compared with polysiloxane-bound 9d′ indicating a non-rigid behavior of the complexes in the matrix.
    Notizen: Mit den Liganden PhP(R)CH2D [R = (CH3O)3Si(CH2)3; D = CH2OCH3: (1b); D = Tetrahydrofuryl (1c); D = 1,4-Dioxanyl (1d)] sind (Ether-phosphan)ruthenium(II)-Komplexe zugänglich, die durch Copolymerisation mit Si(OEt)4 in die entsprechenden Polysiloxan-gebundenen Spezies überführt werden. Die löslichen Komplexe cis,cis,trans-Cl2Ru(CO)2(P ∼ O)2 (3b) und HRuCl(CO)(P ∼ O)3 (5b) werden mit NaBH4 zu cis,cis,trans-H2Ru(CO)2(P ∼ O)2 (4b) bzw. H2Ru(CO)(P ∼ O)3 (6b) umgesetzt (P ∼ O = η1-P koordiniert; = η2- koordiniert). Zugabe von Si(OEt)4 und Wasser führt zu einer basenkatalysierten Hydrolyse der Alkoxygruppen am Silicium und zur Abscheidung der immobilisierten Komplexe 4b′, 6b′. Die durch diese Sol-Gel-Variante gebildete Polysiloxanmatrix wird 29Si—CP-MAS-NMR-spektroskopisch durch Quantifizierung der auftretenden Silylspezies beschrieben. 4b′ reagiert mit Kohlenmonoxid zu Ru(CO)3(P ∼ O)2 (7b′). Polysiloxan-gebundene Chelat-Komplexe des Typs Cl2Ru()2 (9c′, d′) und Cl2Ru()(P ∼ O)2 (10b′, c′) sind durch Reaktion von 1b-c mit Cl2Ru(PPh3)3 (8) und nachfolgender Copolymerisation mit Si(OEt)4 zugänglich. 9c′, d′ und 10b′, c′ reagieren mit einem Äquivalent CO zu Cl2Ru(CO)()(P ∼ O) (12b′-d′). Mit überschüssigem CO erhält man die Spezies all-trans-Cl2Ru(CO)2(P ∼ O)2 (14b′-d′), die sich thermisch zu den cis,cis,trans-konfigurierten Isomeren 3b′-d′ umlagern. Ein Vergleich der Anisotropie der 31P-chemischen Verschiebung in kristallinem Cl2Ru()2 (9a, R = Ph, D = CH2OCH3) und Polysiloxan-gebundenem 9d′ deutet auf eine Beweglichkeit der Komplexe in der Matrix hin.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/zaac.19946200703
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