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  • 1
    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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  • 2
    ISSN: 0044-2313
    Keywords: Silylenes ; 1,3-Diselena-2,4-disiletane ; 1,3-Ditellura-2,4-disiletane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Silylene Reactions with Selenophene and a Tellurophene: Formation and Structures of a 1,3-Diselena-2,4-disiletane and a 1,3-Ditellura-2,4-disiletane [1]Di-tert-butylsilylene, generated by photolysis of hexa-tert-butylcyclotrisilane, reacts with selenophene or 2,5-dimethyltellurophene by chalcogen abstraction to furnish the 1,3-diselena-2,4-disiletane 6 and 1,3-ditellura-2,4-disiletane 7 ring systems. The X-ray structure analyses of 6 and 7 reveal strictly planar four-membered rings with the smaller endocyclic angles at the chalcogen and the larger angles at the silicon atoms.
    Notes: Photolytisch aus Hexa-tert-butylcyclotrisilan erzeugtes Di-tert-butylsilylen reagiert mit Selenophen oder 2,5-Dimethyltellurophen unter Chalkogenabstraktion zum 1,3-Diselena-2,4-disiletan 6 und 1,3-Ditellura-2,4-disiletan 7. Die Röntgenstrukturanalysen von 6 und 7 zeigen das Vorliegen planarer Vierringe mit den kleineren endocyclischen Winkeln an den Chalkogen- und den größeren an den Siliciumatomen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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