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  • 1
    Electronic Resource
    Electronic Resource
    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
    Keywords: Sulfur dioxide ; Rhodium complexes ; Ether-phosphanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290920
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  • 2
    Electronic Resource
    Electronic Resource
    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
    Keywords: Ether-phosphanes ; Ruthenium complexes ; Polysiloxane matrices ; CP-MAS NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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′.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921251110
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  • 3
    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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  • 4
    Electronic Resource
    Electronic Resource
    Cage-Structured Triplatinacyclophanes (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 679-685 
    Details
    ISSN: 1434-1948
    Keywords: Cage compounds ; Metallacyclophanes ; P ligands ; Platinum ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the tris(triflate) 4 (Scheme 1) has been achieved by means of a straightforward three-step reaction sequence. After initial lithiation of mesitylene, treatment of the obtained trilithium compound C6H3(CH2Li)3 (2) with oxirane results in the formation of 1,3,5-tris(3-hydroxypropyl)benzene (3), which is then transformed to 4 by reaction with (CF3SO2)2O in the presence of pyridine. Whereas 4 reacts with Na2[Os(CO)4] in a somewhat complicated manner, similar reactions with Na[Re(CO)5] and LiPPh2 give the hydrocarbon-bridged tris(rhenium) complex C6H3[(CH2)3Re(CO)5]3 (5) and the tris(phosphane) C6H3[(CH2)3PPh2]3 (6), respectively. Employing the high-dilution method, from 6 and Cl2Pt(NCPh)2 the nanoscaled tri- and hexaplatinacyclophanes 7 and 9 are available. Owing to the optimal geometry and flexibility of the cage in 7, 1,2-dichloroethane can be reversibly encapsulated. The molecular structure of 7 · 7 1,2-Cl2C2H4 was determined by an X-ray structure analysis. The utility of the reactive metal centers in 7 has been demonstrated by replacing the chloro ligands by acetonitrile to give the cationic platinacyclophane 8, in which, according to NMR studies, the cage-like structure is preserved.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Stoichiometric and Catalytic Reactions of the Polysiloxane-Bound (Ether-Phosphine)Rhodium(I) Complex [ClRh(PO)(P ∼ O)] in InterphasesSupported organometallic complexes part 14. Part 13: E. Lindner, A. Jäger, F. Auer, W. Wielandt, P. Wegner, J. Mol. Catal. in press.Dedicated to Professor H. D. Kaesz on the occasion of his 65th birthdayNotation used in this paper: Fn = functionality; D, T, and Q denote alkoxysilanes with two, three, and four Si-O bonds, respectively; the superscript denotes the number of Si—O—Si bonds formed during the sol-gel process and is a measure of cross-linkage; for example, T0 = MeSi(OMe)3. P∼O: η1-P-coordinated ether-phosphine ligand; PO: η2-O,P-chelating ether-phosphine ligand. Cy = cyclohexyl, COE = cyclooctene, Py = pyridine. (1997)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 1833-1845 
    Details
    ISSN: 0947-6539
    Keywords: immobilized catalysts ; polysiloxanes ; P ligands ; rhodium ; sol-gel processes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of four equivalents of the monomeric trimethoxysilyl(T)-functionalized ether-phosphine ligand CyP(CH2CH2OCH3)(CH2)3SiR3 (R = OMe [1 a(T0)], Me [1 b]) with [{μ-ClRh(COE)2}2] yielded the monomeric pseudo 14 electron rhodium(I) complexes [ClRh(PO)(P∼O)] (2a(T0)2, 2 b). For the sol-gel process the complex 2 a(T0)2 was protected by introduction of the volatile, reversibly binding ligand pyridine. Thus, the monomeric compound 2 a(T0)2 was co-condensed with two and eight equivalents of the co-condensation agent MeSi(OMe)2(CH2)6(MeO)2SiMe (D0-C6-D0) to give the polysiloxane-bound congeners 2(Tn)2(Di-C6-Di)y (y = 2 and 8, respectively; i = 0-2; n = 0-3). The polysiloxane-bound complex 2(Tn)2-(Di-C6-Di)2 was treated with a variety of small molecules in the gas/solid and liquid/solid interphases. It was shown that a facile cleavage of the Rh-O bond in the ether-phosphine chelate occurred even in the solid state. The reaction of 2(Tn)2-(Di-C6-Di)2 with carbon monoxide, carbon disulfide, and diphenylacetylene resulted in the irreversible coordination of the molecule to the metal. In the presence of pyridine, the polysiloxane-bound complex 2(Tn)2-(Di-C6-Di)2 oxidatively added hydrogen to give the octahedrally configurated complex [ClRhH2(Py)(P ∼ O)2] [6(Tn)2(Di-C6-Di)2]. Treatment of dry 2(Tn)2-(Di-C6-Di)2 with ethene led to the reversible formation of the corresponding complex. Although the materials display low surface areas, at least 75% of the rhodium centers within the matrix are accessible to the rather bulky tolan molecules. The complexes 2(Tn)2(Di-C6-Di)y (y (y = 2, 8) show high activities and selectivities in the hydrogenation of tolan. The conversion was found to depend markedly on the amount of co-condensate (D0-C6-D0) and on the polarity of the solvent. The polysiloxane-bound complexes 2(Tn)2(Di-C6-Di)y are more active than their monomeric congener 2 a(T0)2.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19970031116
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  • 6
    Electronic Resource
    Electronic Resource
    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
    Keywords: Ether-phosphanes ; ruthenium complexes ; polysiloxane-matrices ; heteronuclear CP-MAS NMR spectroscopy, Chemical Shift Anisotropy (CSA) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 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.
    Notes: 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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19946200703
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