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  • 2000-2004  (2)
  • 1985-1989  (5)
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  • 1
    Electronic Resource
    Electronic Resource
    Hydrido-silyl complexes, Part VIII. Photochemical reaction of [Fe(CO)3H(PR′3)SiR3] with silanes, HSiR3: Influence of PR′3 and SiR3 on formation and structures of bis-silyl complexes [Fe(CO)3(PR′3)(SiR3)2] (1986)
    Springer
    Transition metal chemistry 11 (1986), S. 268-271 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Upon u.v. irradiation of [Fe(CO)4(PR 3 ′ )] with HSiR3 (HSiR3 = HSiMePh2, PR′3 = PPh3; HSiR3 = HSiMe2Cl, PR′3 = PPh3 or PMe2Ph; HSiR3 = HSiMeCl2, PR′3 = PPh3, PMePh2, PMe2Ph or PMe3; HSiR3 = HSiCl3, PR′3 = PPh3, PMePh2, PMe2Ph, PMe3 or PBu 3 n ) the corresponding hydridosilyl complexes [Fe(CO)3H(PR′3)SiR3] are formed. The complexes have themer configuration with acis disposition of the hydride and the silyl ligands. Prolonged irradiation with an excess of silane results in the formation of bis-silyl complexes [Fe(CO)3(PR3)(SiR3)2], if electron density at the metal is not too high. Thus, [Fe(CO)3H(PPh3)SiMePh2] and [Fe(CO)3-H(PMe2Ph)SiMe2Cl] can be obtained but not the corresponding bis-silyl complexes. Most bis-silyl complexes are obtained asmer-isomers with acis-arrangement of the silyl ligands. Only for [Fe(CO)3(PR′3)(SiCl3)2] with small phosphine ligands (PR′3 = PMe3 or PMe2Ph) is thefac-isomer formed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00959930
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  • 2
    Electronic Resource
    Electronic Resource
    Übergangsmetall-Silyl-Komplexe, 18 Hydrido-Silyl- und Bissilyl-Komplexe des Eisens mit verbrückenden oder chelatisierenden Diphosphinoethan-Liganden (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 879-887 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complexes [mer-(CO)3Fe(H)SiR3]2(dppe) (1) (dppe=Ph2PCH2-CH2PPh2), [mer-(CO)3Fe(SiR3)2]2(dppe) (2), (CO)2(dppe)Fe(H)-Sir3 (3), and (CO)2(dppe)Fe(SiR3)2 (6) are synthetized by several routes: by photochemical reaction of dppe-substituted iron carbonyls with HSiR3, by thermal reaction of (CO)4Fe(H)SiR3 or (CO)4Fe(SiR3)2 with dppe, or by exchange of the silyl groups. The dinuclear complexes 1 and 2 can be converted to the mononuclear complexes 3 and 6. The choice of the most suitable method of preparation depends essentially on the nature of the silyl ligand. Bissilyl complexes (2 or 6) are only obtained if SiR3=SiCl3 or SiMeCl2. In solution the complexes 3 are fluxional. In the crystalline state 3d (SiR3=SiMe3) shows a distorted octahedral geometry. The silyl group has trans orientation to one of the phosphorus atoms and cis to the hydride ligand, which in turn is trans to one of the carbonyls.
    Notes: Komplexe [mer-(CO)3Fe(H)SiR3]2(dppe) (1) (dppe=Ph2PCH2CH2PPh2), [mer-(CO)3Fe(SiR3)2]2(dppe) (2), (CO)2(dppe)Fe(H)-SiR3 (3) und (CO)2(dppe)Fe(SiR3)2 (6) können nach mehreren Methoden synthetisiert werden: durch photochemische Umsetzung von dppe-substituierten Eisencarbonylen mit HSiR3, durch thermische Umsetzung von (CO)4Fe(H)SiR3 oder (CO)4Fe(SiR3)2 mit dppe oder durch Silylgruppenaustausch. Die zweikernigen Komplexe 1 und 2 lassen sich in die einkernigen Komplexe 3 und 6 umwandeln. Die Wahl der jeweils günstigsten Darstellungsmethode hängt entscheidend von der Art des Silylrestes ab. Bissilyl-Komplexe (2 oder 6) werden nur mit SiR3=SiCl3 oder SiMeCl2 erhalten. Die Komplexe 3 sind in Lösung fluktuierend. Im kristallinen Zustand ist 3d (SiR3=SiMe3) verzerrt oktaedrisch koordiniert, der SiMe3-Rest steht trans zu einem der Phosphoratome und cis zum Hydrid-Liganden, welcher seinerseits trans zu einem der Carbonyle angeordnet ist.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200603
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  • 3
    Electronic Resource
    Electronic Resource
    Übergangsmetall-Silyl-Komplexe, 201) Untersuchungen zur Reaktivität der anionischen Silyl-Komplexe [Fe(CO)3(PR′3)SiR3]- (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1079-1085 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition-Metal Silyl Complexes, 201). - Investigations on the Reactivity of the Anionic Silyl Complexes [Fe(CO)3(PR3′)SiR3[-Phosphane-substituted anionic silyl complexes [Fe(CO)3(PR′3)SiR3]- (1) are distinctly more reactive than their tetracarbonyl analoga, particularly towards metal or metal-complex halides. Their solution structure depends on the corresponding cation, with which they are able to form contact ion pairs. Reaction of 1 with CH3I, Me2SiHCl or Me3SnCl (R″3EX) yields phosphanesubstituted alkyl silyl, bissilyl or silyl stannyl complexes mer-Fe(CO)3(PR′3)(ER″3)SiR3. By reaction of 1 with (Ph3PAgCl)4, Ph3PAuCl, PhHgBr or HgBr2 (LnMX) stable hetero-binuclear complexes mer-Fe(CO)3(PR′3)SiR3)MLn can be prepared, which contain unsupported Fe-Ag-, Fe-Au-, or Fe-Hg bonds. X-ray structure analysis of Fe(CO)3(PPh3)(SiMePh2)AuPPh3 (6) (Fe-Au 255.1 (1), Fe-Si 235.7 (3) pm) reveals that the SiMePh2 and the PPh3 ligand are cis oriented to the Fe-Au bond.
    Notes: Die phosphansubstituierten anionischen Silyl-Komplexe [Fe(CO)3(PR′3)SiR3]- (1) sind besonders gegenüber Metall- oder Metallkomplex-Halogeniden deutlich reaktiver als ihre Tetracarbonyl-Analoga. Ihre Struktur in Lösung hängt vom jeweiligen Kation ab, mit dem sie Kontaktionenpaare ausbilden können. Reaktion von 1 mit CH3I, Me2SiHCl oder Me3SnCl (R″3EX) ergibt phosphansubstituierte Alkyl-Silyl-, Bissilyl- oder Silyl-Stannyl-Komplexe mer-Fe(CO)3(PR′3)(ER″3)SiR3. Durch Umsetzung von 1 mit (Ph3PAgCl)4, Ph3PAuCl, PhHgBr oder HgBr2 (LnMX) können die stabilen Hetero-Zweikernkomplexe mer-Fe(CO)3(PR′3)-(SiR3)MLn dargestellt werden, die unverbrückte Fe-Ag-, Fe-Au- oder Fe-Hg-Bindungen enthalten. Die Röntgenstrukturanalyse von Fe(CO)3(PPh3)(SiMePh2)AuPPh3 (6) (Fe-Au 255.1 (1), Fe-Si 235.7(3) pm) zeigt, daß der SiMePh2- und der PPh3-Ligand cis zur Fe-Au-Bindung angeordnet sind.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200703
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  • 4
    Electronic Resource
    Electronic Resource
    Reactivity of Silyl-Substituted Heterobimetallic Iron-Platinum Hydride Complexes towards Unsaturated Molecules, I Alkyne Insertions into the Platinum-Hydride Bond, Phosphane-Induced σ-Alkenyl-μ-Vinylidene Rearrangements and Formation of μ-Isonitrile Complexes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 241-252 
    Details
    ISSN: 1434-1948
    Keywords: Heterobimetallics ; Hydride complexes ; Alkenyl complexes ; μ-Isonitrile complexes ; Silicon ; Iron ; Platinum ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heterobimetallic hydride complexes [(OC)3Fe{Si(OMe)3}(μ-Ph2PXPPh2)Pt(H)(PR3)] (1a: X = CH2, PR3 = PPh3; 1b: X = NH, PR3 = PPh3; 1c: X = CH2, PR3 = PMePh2) have been prepared by the oxidative addition of [(OC)3Fe(H){Si(OMe)3}(η1-Ph2PXPPh2)] to [Pt(H2C=CH2)(PPh3)2] or by reaction of K[(OC)3Fe{Si(OMe)3}(η1-dppm)] with trans-[Pt(Cl)(H)(PPh3)2]. The solid-state structure of compound 1b has been determined by single-crystal X-ray diffraction. 1-Alkynes such as methylpropiolate or phenylacetylene insert in a regiospecific manner into the Pt-H bond of 1 to yield the σ-alkenyl complexes [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-Ph2PXPPh2)Pt{C(R)=CH2}] (2a: X = CH2, R = CO2Me; 2b: X = NH, R = CO2Me; 3a: X = CH2, R = Ph). Addition of the Pt-H bond of 3a across the triple bond of [D1]phenylacetylene affords [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pt{C(Ph)=C(D)H}] (3a*) having the deuteron trans to platinum (cis addition). This insertion reaction is accompanied by dissociation of the platinum-bonded PR3 ligand and saturation of the vacant coordination site by a dative μ-η2-Si-O→Pt interaction. When 3 is treated with PR3 again, a subsequent phosphane-induced rearrangement leading to vinylidene-bridged complexes [(OC)3Fe{μ-C=C(H)R′}(μ-Ph2PXPPh2)Pt(PR3)] (4a: X = CH2, R′ = Ph, PR3 = PPh3; 4b: X = NH, R′ = Ph, PR3 = PPh3; 4c: X = CH2, R′ = Ph, PR3 = PMePh2; 4d: X = CH2, R′ = p-tolyl, PR3 = PPh3) occurs. Upon purging a solution of 3a with carbon monoxide, the labile CO adduct [(OC)3Fe{Si(OMe)3}(μ-dppm)-Pt(CO){C(Ph)=CH2}] 5a is formed, addition of 2,6-xylyl isocyanide to 2a and 3a affords the isonitrile adducts [(OC)3Fe{Si(OMe)3}(μ-dppm)Pt(CNxylyl){C(R)=CH2}] (5b: R = CO2Me; 5c: R = Ph), respectively. When hydride complex 1a is allowed to react with stoichiometric amounts of aromatic isonitriles, formal elimination of HSi(OMe)3 occurs, yielding the heterodinuclear isonitrile-bridged complexes [(OC)3Fe(μ-C=N-R)(μ-dppm)Pt(PPh3)] (6a: R = 2,6-xylyl; 6b: R = o-anisyl; 6c: R = p-anisyl; 6d: R = p-C6H4NH2) and the bis(isonitrile) complexes [(OC)2(RN≡C)Fe(μ-C=N-R)(μ-dppm)Pt(PPh3)] (7a: R = 2,6-xylyl; 7b: R = p-anisyl). Single-crystal X-ray diffraction studies perfomed on 6a and 6b reveal that the molecular structures of these μ-isonitrile complexes closely resemble the μ-vinylidene complexes 4. The two metal centers are bridged in a symmetric manner by strongly bent CNR ligands, the aromatic groups R being oriented towards the Fe(CO)3 moiety. Electrophilic addition of HBF4 to the basic nitrogen atom of the μ-CNR ligand transforms 6 to the cationic μ-aminocarbyne complexes [(OC)3Fe{μ-CN(H)R}(μ-dppm)Pt(PPh3)][BF4] (8a: R = 2,6-xylyl; 8b: R = p-anisyl; 8c: R = p-C6H4NH2).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Komplexe mit einer η2-μ2-SiO-Brücke; Struktur des Zweikernkomplexes [Fe(CO)3-{μ-Si(OMe)2OMe}(μ-dppm)PdCl](Fe-Pd)Diese Arbeit wurde vom CNRS (Paris), CNR (Rom), von der Kommission der Europäischen Gemeinschaft (Contract Nr. ST2J-0347-C) und der DFG (M. K.) gefördert. (1989)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 101 (1989), S. 1414-1416 
    Details
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19891011027
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  • 6
    Electronic Resource
    Electronic Resource
    Complexes with an η2-μ2-SiO Bridge. Structure of the Bimetallic Complex Financial support from the CNRS (Paris), CNR (Rome), the “Commission of the European Communities” (Contract No. ST2J-0347-C), and the Deutsche Forschungsgemeinschaft (to M.K.) are gratefully acknowledged. (1989)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 28 (1989), S. 1361-1363 
    Details
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.198913611
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  • 7
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    Synthesis and Molecular Structures of Platinum and Mercury Complexes Chelated by (Phenylthiomethyl)silane Ligands (2004)
    Wiley
    Details
    Publication Date: 2004-10-01
    Print ISSN: 0044-2313
    Electronic ISSN: 1521-3749
    Topics: Chemistry and Pharmacology
    Published by Wiley
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