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  • Low-valent compounds  (2)
  • Silylene  (2)
  • 2015-2019
  • 1995-1999  (4)
  • 1
    Electronic Resource
    Electronic Resource
    The Formation of Macrocyclic Compounds Containing Two Ga-Ga Bonds by the Reaction of Tetraalkyldigallane(4) R2Ga-GaR2 [R = CH(SiMe3)2] with Dicarboxylic Acids (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1661-1665 
    Details
    ISSN: 1434-1948
    Keywords: Gallium ; Low-valent compounds ; Macrocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]digallane(4) 1 reacts with dicarboxylic acids like 1,4-benzenedi(methylcarboxylic) acid, 1,4-cyclohexanedicarboxylic acid, 1,6-hexanedicarboxylic acid, and 1,4-butanedicarboxylic acid (adipinic acid) by the release of two equivalents of bis(trimethylsilyl)methane and the retention of the Ga-Ga bond. Products are formed, in which the very short Ga-Ga bonds (237.7 pm on average) are bridged by two carboxylato groups. Two of these moieties are connected in each compound by two spacers (dimethylbenzene, cyclohexane, hexane, or butane) to form macrocyclic compounds with up to 22 atoms in the resultant heteroatomic rings. The dimeric form is also observed in solution. For comparison, the synthesis and structure of the product of the reaction of 1 with 1-adamantanecarboxylic acid is included, which also has the Ga-Ga bond (239.1 pm) bridged by two carboxylato groups.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 2
    Electronic Resource
    Electronic Resource
    Silylene Reactions with Nitrogen Multiple Bonds: Additions and Rearrangements (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1755-1758 
    Details
    ISSN: 1434-1948
    Keywords: Silicon ; Silylene ; Azobenzene ; 1-Adamantyl azide ; Addition reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of the sterically encumbered silylenes R2Si: (R = 2,4,6-Me3C6H2, 2,4,6-iPr3C6H2) with azobenzene are thought to proceed via the [2+1] cycloaddition products, followed by insertion of the N-N single bond into the ortho-C-H bond of one of the phenyl rings or into the C-HMe2 bond of one of the ortho-isopropyl groups to furnish the 1,3-diaza-2-silaindan (4) or 1-aza-2-silaindan (5) derivatives, respectively. The reactions of these silylenes with 1-adamantyl azide seem to proceed through the silanimines and 4-azahomoadamantene intermediates which, by [2+2] cycloadditions, afford the 1,3-diaza-2-silacyclobutane derivatives 11 and 12. The structures of 4, 5, 11, and 12 were determined by X-ray crystallography.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Silylene Reactions with Buta-1,3-diynes: Cycloadditions, Insertions, and Rearrangements (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2301-2307 
    Details
    ISSN: 1434-1948
    Keywords: Multiple bonds ; Silicon ; Silylene ; Cycloadditions ; Insertions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Di-tert-butylsilylene, generated by photolysis of hexa-tert-butylcyclotrisilane 1 or 1,1-di-tert-butyl-trans-2,3-dimethyl-silirane (2), reacts with the 1,3-diyne (tBu-C≡C-)29 to furnish the dialkynylsilane 11 via the isolable alkynylsilirene 10. Photolysis of excess 1 in the presence of 9 furnishes the C-C linked 2,2′-disilirene 12 which, upon prolonged irradiation, rearranges to the 2,5-disilabicyclo[2.2.0]hexa-1(6),3-diene (13). Treatment of 9 with diarylsilylenes, formed by irradiation of hexamethyl-2,2-dimesityltrisilane (3) or hexamethyl-2,2-bis(2,4,6-triisopropylphenyl)trisilane (4), gives the corresponding alkynylsilirenes 14 and 15, respectively. Photolysis of 1 or 2 in the presence of (Me3Si-C≡C-)216 yields the dialkynylsilane 17 which, on further reaction with 2, yields the 2,5-disilabicyclo[2.2.0]hexa-1(6),3-diene (18). Irradiation of 3 in the presence of 16 affords the cis- and trans-isomeric 1,3-dimethylene-2,4-disila-cyclobutane derivatives cis-21 and trans-21, presumably via a 1-silaallene intermediate. The structures of 12, 15, 18, cis-21, and trans-21 have been determined by X-ray crystallography.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 4
    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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