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  • Inorganic Chemistry  (10)
  • 1995-1999  (10)
  • 1
    Electronic Resource
    Electronic Resource
    Silicon Compounds with Strong Intramolecular Steric Interactions. LVIIPart LVI: Ref.[1].. Oxidation and Cycloaddition Reactions of an Unsymmetrically Substituted DisileneDedicated to Professor Manfred Regitz on the occasion of his 60th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 935-939 
    Details
    ISSN: 0009-2940
    Keywords: Disilenes ; Organosilicon compounds ; 1,2,3-Oxadisiliranes ; Dioxadisiletanes ; Cycloaddition reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the unsymmetrically substituted disilene R2Si=SiR′2 (4; R = 2,4,6-Me3C6H2, R′ = 2,4,6-iPr3C6H2) with m-chloroperbenzoic acid (mCPBA) or oxygen furnished the correspondingly substituted 1,2,3-oxadisilirane 5 or 1,3,2,4-dioxadisiletane 6, respectively. The [2 + 2] and [2 + 4] Cycloaddition reactions of 4 with benzophenone and 3,5-di-tert-butyl-1,2-benzoquinone, respectively, proceeded with a high degree of regioselectivity to yield the 1,2,3-oxadisiletane 9 and the 2,3-dihydro-1,4,2,3-benzodioxadisiline 7. The latter product was isolated together with a small amount of an isomeric compound 8 in which the substituents at the silicon atoms are reversed. The molecular structures of the products 5, 6, and 7 were determined by X-ray crystallography.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280914
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  • 2
    Electronic Resource
    Electronic Resource
    Benzil Derivatives as Trapping Reagents for the Monomeric Alkylindium(i) Compound in-c(SiMe3)3 (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1269-1272 
    Details
    ISSN: 0009-2940
    Keywords: Indium ; Clusters ; Low-valent compounds ; Trapping reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetrahedral cluster compound tetrakis[[Tris(trimethylsilyl)methyl]indium(I)] 91) reacts in boiling n-hexane with benzil derivatives (p-X-C6H4)C(O)(p-X-C6H4) (X = H, OMe, Br), to yield the 1,4-cycloadditon products of the monomeric alkylindium(I), In-C(SiMe3)3, in which the In atoms are coordinated by a chelating enediolato ligand, to form a five-membered InO2C2 heterocycle. As shown by two crystal structure determinations (X = H, OMe), the products are dimeric in the solid state, with a four-membered In2O2 heterocycle in the molecular center and both C(SiMe3)3 groups, as well as both enediolato substitutents in a cis arrangement.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300915
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  • 3
    Electronic Resource
    Electronic Resource
    Reaktionen von R2Al—AlR2 (R = CH(SiMe3)2) mit Trimethylsilylazid  -  Insertion in die Al—Al-Bindung und Abbau zum trimeren Dialkylaluminiumazid (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 81-85 
    Details
    ISSN: 0009-2940
    Keywords: Aluminium-aluminium bond ; Insertion of trimethylsilyl azide ; Trimeric dialkylaluminium azide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of R2Al—AlR2 (R = CH(SiMe3)2) with Trimethylsilyl Azide  -  Insertion into the Al—Al Bond and Formation of a Trimeric Dialkylaluminium AzideTetrakis[bis(trimethylsilyl)methyl]dialuminium(4) (1) reacts with trimethylsilyl azide under insertion of one nitrogen atom into the Al—Al bond. As shown by NMR spectra and crystal structure the product contains three and four coordinated Al atoms due to the coordination of the α-nitrogen atom of the azide group to one of the Al atoms. An electronically delocalized N3-system is formed with a N—N bond length of 132.0 pm and a bond order of 1.5 for both N—N bonds. With an excess of trimethylsilyl azide further reaction is observed only under mild irradiation conditions with an exchange of the azide group between Si and Al and formation of Me6Si2 and the dialkylaluminium azide 3, which is better synthesized by the reaction of Me3Si—N3 with Cl—Al[CH(SiMe3)2]2. The sterically highly shielded aluminium azide 3 is a trimer in the solid state showing a non-planar 12-membered Al3N9 heterocycle with short N—N bonds (114 pm).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280112
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  • 4
    Electronic Resource
    Electronic Resource
    Reactions of the Alkylindium(I) Compound In4[C(SiMe3)3]4 with Sulfur and Tellurium: Syntheses of In4S4[C(SiMe3)3]4 and In4Te4[C(SiMe3)3]4 with Indium Chalcogen Heterocubane Structures (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 143-146 
    Details
    ISSN: 0009-2940
    Keywords: Tetraindane(4) ; Indium(I) ; Sulfur ; Tellurium ; Heterocubane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrahedro-Tetrakis[tris(trimethylsilyl)methyl]tetraindane(4) (1) with a tetrahedral In4 molecular center reacts with an excess of elemental sulfur or tellurium in boiling n-hexane to give in an almost quantitative yield the appropriate In4S4 (2) or In4Te4 derivatives (3). Crystal structure determinations revealed distorted In4X4 (X = S, Te) heterocubane molecular centers for both compounds.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290206
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  • 5
    Electronic Resource
    Electronic Resource
    Synthesis of Novel Optically Active Tin Hydrides Containing Chiral Ligands (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1539-1546 
    Details
    ISSN: 0009-2940
    Keywords: Chiral tin hydrides ; Chiral hydrogen donors ; Tin ; Ligand effects ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the chiral tin bromides 1-4 and hydrides 5-8, containing the potentially bidentate, optically active 2-[ (1 S/R)- 1 -dimethylaminoethyl]phenyl and 2 -[( 1 S) - 1 -dimethylamino-2,2-dimethylpropyl]phenyl ligands, is reported. The tin hydrides 5-8, with the tin atom as the stereogenic centre, were isolated as diastereomeric mixtures with diastereomeric ratios of dr = 50:50 up to dr = 80:20. The absolute configuration of ( - ) - (1 S)- 1 - (2-bromophenyl) -2,2-dimethylpropylamine [(S)-10] was determined by single-crystal X-ray structure analysis.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301030
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  • 6
    Electronic Resource
    Electronic Resource
    Compounds of Germanium and Tin, 22 - Reactions of a Silyene with a Germylene and a Stannylene: Formation of a Digermene with an Unusual Arrangement of the Substituents and of a Stannane (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1733-1737 
    Details
    ISSN: 0009-2940
    Keywords: Silicon ; Germanium ; Tin ; Carbene homologues ; Digermene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the diaminosilylene :Si(tBuNCH2CH2NtBu) (5) with the diaminogermylene :Ge(tBuNCH2CH2NtBu) is thought to proceed via a germasilene → silylgermylene rearrangement and dimerisation to furnish the (Z)-1,2-diamino-1,2-disilyldigermene (Z)-9. The X-ray structure analysis of (Z)-9 reveals a long Ge—Ge bond length of 245 pm and a large trans-bent angle of 42°. Air-oxidation of (Z)-9 takes place with retention of configuration at the germanium atoms to provide the corresponding substituted (Z)-2,4-digerma-1,3-dioxetane (Z)-10. Treatment of 5 with the stannylene :Sn[N(SiMe3)2)2 gives, as a final product, the hydridodisilylstannane 12. The structures of (Z)-10 and 12 were also determined by X-ray crystallography.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301205
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  • 7
    Electronic Resource
    Electronic Resource
    Twofold Insertion of Isocyanides into the Ga—Ga Bond of Tetrakis[bis(trimethylsilyl)methyl]digallane(4) (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 897-901 
    Details
    ISSN: 0009-2940
    Keywords: Gallium-Gallium bond ; Isocyanide insertion ; 1,4-Diazabutadiene derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]digallane(4) (1) reacts with tert-butyl or aryl=isocyanides [aryl = phenyl, o-methylphenyl, o-methoxyphenyl, p-methoxyphenyl) by a twofold insertion of the central carbon atoms into the Ga-Ga bond and formation of C-C single bonds. 1,4-Diazabutadiene derivatives bound to two R2Ga groups are formed (2-6), which in contrast to an aluminium analog exhibit only weak interactions between the imine nitrogen atoms and the coordinatively unsaturated gallium atoms as indicated by NMR spectroscopy and the long Ga-N distances in the molecular structures of three products: 2 (R = C6H5), 4 (R = o-MeOC6H4), and 6 (R = CMe3).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290804
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  • 8
    Electronic Resource
    Electronic Resource
    Compounds of Germanium and Tin, 2lPart 20: Ref.[1]. A Tetraaryldigermene with a Short Germanium-Germanium Double Bond and a Nearly Planar Environment of Both Germanium AtomsDedicated to Professor Hans Bürger on the occasion of his 6oth birthday (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 735-738 
    Details
    ISSN: 0009-2940
    Keywords: Germanium ; Digermenes ; Tin ; Germylenes ; Stannylenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of GeCl2 · dioxane with the Grignard reagent RMgBr (R=2-tBu-4,5,6-Me3C6H) furnishes the tetraaryldigermene R2Ge=GeR2 (8). X-ray structure-analysis of 8 reveals a short Ge=Ge double bond, a nearly planar environment of both germanium atoms and extremely widened C—Ge—C angles of 128°. In solution, 8 dissociates into two germylene molecules R2Ge, which can be trapped with oxygen or by [4+1] cycloaddition reactions with 1,4-dihetero-1,3-dienes. A similar cycloadduct of a stannylene wa obtained by thermolysis of (R′2Sn)3 (R′=2,4,6-iPr3C6H2), in the presence of a 1,4-diazabutadiene and characterized by an X-ray structure-analysis.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300610
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  • 9
    Electronic Resource
    Electronic Resource
    Umsetzungen des Tetrakis[bis(trimethylsilyl)methyl]dialans(4) mit Methylisothiocyanat und Phenylisocyanat - Insertion in die Al—Al-Bindung bzw. Fragmentierung (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 373-379 
    Details
    ISSN: 0044-2313
    Keywords: Al—Al bond ; insertion of isontrile ; isocyanate trimerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Tetrakis[bis(trimethylsilyl)methyl]dialane(4) with Methylisothiocyanate and Phenylisocyanate - Insertion into the Al—Al Bond and FragmentationTetrakis[bis(trimethylsilyl)methyl]dialane(4) 1 reacts with methyl isothiocyanate under cleavage of the C=S double bond and insertion of the remaining isonitrile fragment into the Al—Al bond. As shown by crystal structure determination a three-membered AlCN heterocycle (4) is formed by the interaction of the nitrogen lone pair with one unsaturated Al atom leading to an acute angle at the aluminium center N—Al—C of 36.6°. In contrast the reaction with the hard base phenyl isocyanate yields a mixture of many unknown compounds, from which only one (5) could be isolated in a very poor yield. The crystal structure of 5 reveals only one dialkyl aluminium fragment and a chelating ligand formed by the trimerization of the isocyanate under loss of one CO group and addition of a hydrogen atom. 5 was also synthesized by the specific reaction of the chloro dialkyl aluminium compound (R = CH(SiMe3)2) with Li[H5C6—N=C(O)—N(C6H5)—C(O)—N(H)—C6H5].
    Notes: Tetrakis[bis(trimethylsilyl)methyl]dialan(4) 1 reagiert mit Methylisothiocyanat unter Aufbrechen der C=S-Doppelbindung und Insertion des verbleibenden Isonitril-Fragments in die Al—Al-Bindung. Die Kristallstruktur des Produkts (4) zeigt einen dreigliedrigen AlCN-Heterozyklus, der durch die Wechselwirkung des freien Elektronenpaares am Stickstoffatom mit einem ungesättigten Al-Atom entsteht und am Metallatom einen außerordentlich spitzen Winkel von 36,6° aufweist. Setzt man als härtere Base Phenylisocyanat im Überschuß mit dem Dialan(4) 1 um, entsteht dagegen ein unübersichtliches Produktgemisch, aus dem sich in geringer Ausbeute eine Verbindung (5) isolieren läßt. Die Kristallstruktur von 5 zeigt, daß nur ein Dialkylalanyl-Rest im Molekül vorhanden ist und das Isocyanat unter Verlust einer C=O-Gruppe sowie Aufnahme eines Protons zu einem an das Al-Atom koordinierten Chelatliganden trimerisiert. 5 wurde gezielt auch durch Umsetzung des entsprechenden Chloralans mit dem Lithiumsalz des Liganden Li[H5C6—N=C(O)—N(C6H5)—C(O)—N(H)—C6H5] erhalten.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19966220228
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  • 10
    Electronic Resource
    Electronic Resource
    Die Reaktionen von R2Al—AlR2 und R2In—InR2 mit Benzoesäure - Synthese und Kristallstruktur von R2Al(μ-H)(μ-O2C—C6H5)AlR2 und RIn(μ-O2C—C6H5)4InR [R = CH(SiMe3)2]Professor Joachim Strähle zum 60. Geburtstag gewidmet (1997)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 883-891 
    Details
    ISSN: 0044-2313
    Keywords: Aluminium ; indium ; Al—Al bond ; In—In bond ; benzoato bridges ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Reactions of R2Al—AlR2 and R2In—InR2 with Benzoic Acid - Synthesis and Crystal Structure of R2Al(μ-H)(μ-O2C—C6H5)AlR2 and RIn(μ-O2C—C6H5)4InR [R = CH(SiMe3)2]Tetrakis[bis(trimethylsilyl)methyl]dialane(4) 1 reacts with benzoic acid by the oxidative cleavage of the Al—Al bond: The Al atoms are inserted into the O—H bond of the acid and the proton is reduced to a hydride anion. As shown by a crystal structure determination, the product 4 shown an unprecedented structure with both dialkylaluminium fragments unsymmetrically bridged by the hydrogen atom and a benzoato group. 4 can be described as a model compound for the first step of the hydrolysis of compounds with low-valent Al atoms as well as elemental aluminium itself. The diindane(4) analogue of 1 (2) and benzoic acid yield, however, elemental indium and mixed alkyl benzoato indium derivatives, from which bis(trimethylsilyl)methyldi(benzoato)indium 9 has been characterized by a crystal structure determination. 9 consists of a dimer with a remarkable cage structure, in which both monoalkylindium groups are interconnected by four benzoato-O,O′ bridges.
    Notes: Tetrakis[bis(trimethylsilyl)methyl]dialan(4) 1 reagiert mit Benzoesäure unter oxidativer Öffnung der Al—Al-Bindung, wobei sich formal die Al-Atome in die O—H-Bindung der Säure einschieben und das Proton zu einem Hydridion reduzieren. Die beiden Dialkylaluminium-Fragmente des daraus erhaltenen Produkts 4 werden, wie durch Kristallstrukturbestimmung gezeigt wird, in bisher unbekannter Weise durch das Wasserstoffatom und eine Benzoatogruppe unsymmetrisch miteinander verbrückt. 4 läßt sich als Modellverbindung für die erste Stufe der Hydrolyse von Derivaten mit niederwertigen Al-Atomen und elementarem Aluminium beschreiben. Das zu 1 analoge Diindan(4) 2 ergibt dagegen mit Benzoesäuren unter Abscheidung von elementarem Indium gemischte Alkyl-benzoatoindium-Verbindungen. Bis(trimethylsilyl)methyl-di(benzoato)indium 9 wird kristallstrukturanalytisch untersucht; es liegt als Dimeres mit einer Käfigstruktur vor, in der zwei Monoalkylindium-Reste über vier Benzoato-O,O′-Brücken miteinander verbunden werden.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.199762301139
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