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  • 1
    Electronic Resource
    Electronic Resource
    Aspects of the Chemistry of the Cyclic Phosphonium Salt [Ph2PaP(Cl)N(SiMe3)C(tBu)=CbH(Pa-Cb)]Cl and the Related Diazadiphosphetidine [ClPaN(R)P(Cl)NbR(Pa-Nb)] [R = C(tBu)=C(H)SiMe3] (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 751-760 
    Details
    ISSN: 1434-1948
    Keywords: Phosphorus chemistry ; Phosphonium salts ; Diazadiphosphetidines ; Phosphazoles ; 1-Azaallyl compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report the preparation of the novel phosphonium salts [Ph2PaP(NR′2)N(R)C(tBu)=CbH]A(Pa-Cb) (2a; R′ = Et, R = SiMe3, A = Cl; 2b: R′ = Me, R = SiMe3, A = Cl; 2c: R = Et, R′ = SiMe3, A = [OSO2CF3]; 2d: R′ = Et, R = SiMe3, A = [BPh4]; 4: R′ = Et, R = H, A = Cl) and trans-1,3,2,4-diazadiphosphetidines R′2NPaN(R)P(NR′2)Nc(R)(Pa-Nc) [3a: R′ = Et, R = C(tBu)=C(H)PPh2; 3b: R′ = Me, R = C(tBu)=C(H)PPh2; 7: R′ = Me, R = C(tBu)=C(H)SiMe3]. Reaction of 3a with Cu2I2 led to the P- and P,P′-centred complexes [Cu(I)(3a)] (5a) and [{Cu(I)}2(3b)] (5b) [R = C(tBu)=C(H)PPh2]. The phosphazole NaC(tBu)C(H)CcPaN(Me)(CH2)2NcMe(Na-Pa)(Cc-Nc) (8) was obtained by a remarkable hetero-cycloaddition reaction from the diazadiphosphetidine ClPaN(R)P(Cl)NbR(Pa-Nb) [6: R = C(tBu)=C(H)SiMe3] and the electron-rich olefin [=CaN(Me)(CH2)2NaMe(Ca-Na)]2 and was oxidised with S8 yielding NaC(tBu)C(H)CcPa-(S)N(Me)(CH2)2NcMe(Na-Pa)(Cc-Nc) (9). Compounds 2-9 were characterised by multinuclear NMR spectroscopy, mass spectrometry for 5-9, while single-crystal X-ray diffraction data are provided for 3a and 5a.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    [Ga4{C(SiMe3)3}4] mit tetraedrischem Ga4-GerüstDiese Arbeit wurde von der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie gefördert. (1992)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 104 (1992), S. 1378-1380 
    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.19921041016
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  • 3
    Electronic Resource
    Electronic Resource
    Synthese und Kristallstruktur eines μ-Methylen-μ-hydrido-dialanats [R2Al(μ-CH2)(μ-H)AlR2]- (R = CH(SiMe3)2) (1994)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 856-862 
    Details
    ISSN: 0044-2313
    Keywords: Methylene bridged dialuminium compounds ; reaction with tert-butyl lithium ; Al—C—Al and Al—H—Al bridge ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of a μ-Methylene-μ-hydrido-dialanate [R2Al(μ-CH2)(μ-H)AlR2]- (R = CH(SiMe3)2)tert-Butyl lithium reacts with the recently synthesized methylene bridged dialuminium compound [(Me3Si)2CH]2Al—CH2—Al[CH(SiMe3)2]2 2 in the presence of TMEDA under β-elimination; the thereby formed hydride anion is bound in a chelating manner by both unsaturated aluminium atoms forming a 3c-2e-Al—H—Al bond. The crystal structure of the product shows two independent molecules differing only slightly in bond lengths and angles, but significantly in conformation. While one of the Al2CH heterocycles deviates little from planarity with a rough C2 symmetry for the whole anion, the other one is folded with an angle of 21.1° and the arrangement of the substituents is best described by Cs symmetry.
    Notes: tert-Butyllithium reagiert mit der methylenverbrückten Dialuminiumverbindung [(Me3Si)2CH]2Al—CH2—Al[CH(SiMe3)2]2 2 in Gegenwart von TMEDA unter β-Eliminierung; das dabei entstehende Hydridion wird von den beiden dreifach koordinierten, ungesättigten Aluminiumatomen chelatartig unter Ausbildung einer 3z-2e-Al—H—Al-Bindung gebunden. Im Kristall liegen zwei unabhängige Moleküle vor, die sich nur geringfügig in Bindungslängen und -winkeln, deutlich aber in ihrer Konformation voneinander unterscheiden. Während einer der vorliegenden Al2CH-Heterozyklen mit einem Faltungswinkel von 3,8° nur wenig von der Planarität abweicht und das Anion annähernd C2-Symmetrie aufweist, besitzt der andere mit 21,1° eine deutlicher gewinkelte Struktur und die Anordnung der Substituenten entspricht näherungsweise einer Cs-Symmetrie.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19946200518
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  • 4
    Electronic Resource
    Electronic Resource
    Umsetzungen von Ga2Br4 · 2 Dioxan mit (Trimethylsilyl)methyllithium und Neopentyllithium - Synthese und Kristallstruktur von Lithiumtetraalkylgallanaten(III) mit Li-C-Ga-Brücke (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 279-284 
    Details
    ISSN: 0009-2940
    Keywords: Digallium tetrabromide · 2 dioxane, reaction with alkyalithium compounds ; Lithium tetraalylgallantes ; Lithium-carbon-gallium bridge ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of Ga2Br4 · 2 Dioxane with (Trimethylsilyl)methyllithium and Neopentyllithium  -  Synthesis and Molecular Structure of Lithium Tetraalkylgallanates(III) with Li-C-Ga BridgesGa2Br4 · 2 dioxane reacts with (trimethylsilyl)methyllithium or neopentyllithium to yield in n-pentane/diethyl ether solution besides elemental gallium exclusively the disproportionation product trialkylgallane. In pure n-pentane the dioxane adducts of the corresponding lithium tetraalkylgallantes (R = —CH2SiMe3 2; R = —CH2CMe3 4) are formed. 2 and 4 are also synthesized by the reaction of GaBr3 with alkyl lithium in the molar ratio 1:4. The crystal structure of 2 shows a dioxane-bridged dimer and Li-C-Ga bridges with lithium probably bound by the C-H s̰-bonds of the central carbon atoms.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240207
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  • 5
    Electronic Resource
    Electronic Resource
    Darstellung hochsubstituierter Aromaten über Diels-Alder-Reaktionen mit 2H-Pyran-2-onen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1347-1355 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Highly Substitued Benzenes via Diels-Alder Reactions with 2H-Pyran-2-onesThe 2H-pyran-2-ones (α-pyrones) 1 react as dienes in Diels-Alder reactions with acetylene derivatives. The primarely formed cycloadducts immediately aromatize to benzenes by CO2 elimination. Thus, methyl acetylenedicarboxylate (2a) gives dimethylphthalates 3, and methyl acetylenediphosphonate (2b) gives dimethyl 1,2-phenylenediphosphonates 8. The reactions of 1-(dimethylamino)-1-methoxyethene (9) with 1 regioselectively produce N,N-dimethylanilines 10 and isomeric homophthalate derivatives 12. Naphthoquinones 14 could be generated from 1,4-benzoquinone (13) and 1 in the presence of acetic anhydride and Pd/C. Hydroxy-2H-pyran-2-ones 4 react via their trimethylsilyl ether 6 analogously with 2a to give dimethyl (trimethylsiloxy)-phthalates 7 which are easily converted to phenols 5 by acidcatalyzed hydrolysis.
    Notes: Acetylenderivate reagieren mit 2H-Pyran-2-onen (α-Pyronen) 1 als Dien-Komponenten primär zu Diels-Alder-Cycloadditionsprodukten, die sofort unter CO2-Abspaltung zu Benzolderivaten aromatisieren. So werden mit Acetylendicarbonsäure-dimethylester (2a) Phthalsäure-dimethylester 3 und mit Acetylenbis(phosphonsäure-dimethylester) (2b) 1,2-Phenylenbis(phosphonsäure-dimethylester) 8 erhalten. 1-(Dimethylamino)-1-methoxyethen (9) sowie 2,3-Pentadiendisäure-dimethylester (11) bilden mit 1 regioselektiv N,N-Dimethylaniline 10 sowie isomere Homophthalsäure-Derivate 12. Aus 1,4-Benzochinon (13) und 1 entstehen in Gegenwart von Acetanhydrid und Pd/C Naphthochinone 14. Hydroxy-2H-pyran-2-one 4 lassen sich über ihre Trimethylsilylether 6 mit 2a zu den (Trimethylsiloxy)phthalsäure-dimethylestern 7 umsetzen, deren säurekatalysierte Hydrolyse glatt zu den Phenolen 5 führt.
    Additional Material: 13 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200813
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  • 6
    Electronic Resource
    Electronic Resource
    Bis[bis(trimethylsilyl)methyl]galliumbromid und monomeres {Bis[bis(trimethylsilyl)methyl]gallium}[tris(trimethylsilyl)silyl]tellurid [(Me3Si)2CH]2Ga-TeSi(SiMe3)3 (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1547-1551 
    Details
    ISSN: 0009-2940
    Keywords: Gallium telluride, monomeric elementorganic ; Metathesis reaction between a digallium(4) and a ditellane derivative ; Gallium-tellurium π interaction, Tellurium compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis[bis(trimethylsilyl)methyl]gallium Bromide and Monomeric {Bis[bis(trimethylsilyl]methyl]gallium} [Tris(trimethylsilyl)silyl]telluride [(Me3Si)2CH]2Ga-TeSi(SiMe3)3Bis[bis(trimethylsilyl)methyl]gallium bromide GaBr[CH(SiMe3)2]2 (4), prepared from Ga2Br4 · 2 dioxane and bis(trimethylsilyl)-methyllithium in the molar ratio of 1:3, reacts with the sterically high-shielded lithium tris(trimethylsilyl)silyltelluride · DME to yield [(Me3Si)2CH]2Ga-TeSi(SiMe3)3 (5). 5 can also be synthesized by a metathetic reaction between tetrakis-[bis(trimethylsilyl)methyl]digallium(4) and bis[tris(trimethylsilyl)silyl]ditellane in toluene at 100°C. A crystal structure determination shows the compound to be monomeric in the solid state and the atoms of the central C2Ga-TeSi moiety to lie in the mirror plane of the molecule. The short Ga-Te distance of 253.5(1) pm as well as a hindered rotation (ΔErot ≍ 50 kJ · mol-1) as detected by NMR measurements might be interpreted in terms of a π interaction between gallium and tellurium.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250706
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  • 7
    Electronic Resource
    Electronic Resource
    Synthese und Kristallstruktur von Li2[(Me3SiCH2)3Al—CH2—Al(CH2SiMe3)3]  -  ein Addukt des Dilithiomethans CH2Li2? (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1511-1516 
    Details
    ISSN: 0009-2940
    Keywords: Dilithium bis(aluminate) ; methylene-bridged ; Hexacoordinated carbon atom ; Dilithiomethane derivative ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Crystal Structure of Li2[(Me3SiCH2)3Al—CH2—Al(CH2SiMe3)3] - a Dilithiomethane Derivative?Reaction of (trimethylsilyl)methyllithium with the methylene-bridged aluminium tetrachloride Cl2Al—CH2—AlCl2 yields dilithium methylenebis[tris(trimethylsilylmethyl)aluminate] (2) as the only isolable product. All attempts for preparing the tetraalkyl analogue have been unsuccessful. The crystal structure of 2 exhibits a hexacoordinated central carbon atom with short Li—C distances. Both lithium atoms and the methylene hydrogens of the Al—CH2— Al unit are almost coplanar. The discussion of the structure and properties leads to the attractive description of 2 as an adduct of tris(trimethylsilylmethyl)-aluminium to dilithiomethane CH2Li2.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240705
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  • 8
    Electronic Resource
    Electronic Resource
    Solvensfreies Tris(trimethylsilyl)methyllithiumDiese Arbeit wurde von der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie gefördert. (1991)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 103 (1991), S. 339-341 
    Details
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19911030328
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  • 9
    Electronic Resource
    Electronic Resource
    [Ga4{C(SiMe3)3}4] with a Tetrahedral Ga4 SkeletonThis work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. (1992)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 31 (1992), S. 1364-1366 
    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.199213641
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  • 10
    Electronic Resource
    Electronic Resource
    Solvent-free Tris(trimethylsilyl)methyllithiumThis work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. (1991)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 30 (1991), S. 324-326 
    Details
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.199103241
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