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Disilynes. III [1] A Relatively Stable Disilyne RSi≡SiR (R = SiMe(Si t Bu 3 ) 2 )
Author(s) -
Wiberg Nils,
Vasisht Sham Kumar,
Fischer Gerd,
Mayer Peter
Publication year - 2004
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200400177
Subject(s) - adduct , chemistry , heptane , silylation , medicinal chemistry , ring (chemistry) , oxygen atom , stereochemistry , crystallography , molecule , catalysis , organic chemistry
Abstract The disilyne R**Si≡SiR** (R** = SiMe(Si t Bu 3 ) 2 ), prepared as the first isolable and realtively stable silicon compound with a SiSi triple bond two years ago by dehalogenation of trans ‐R**ClSi=SiClR** with LiC 10 H 8 in thf at ‐78 °C (calc.: Si≡Si distance 2.072Å, Si‐Si≡Si bond angle 148°), forms with CH 2 =CH 2 a [2+2] and with CH 2 =CH‐CH=CH 2 a [2+4] cycloadduct. The ethene adduct takes up oxygen very easily with change of the Si=Si group into a SiOSiO ring with formation of R**Si(μ‐O)(μ‐O)(μ‐C 2 H 4 )SiR**. By heating the disilyne in heptane to ca. 50 °C in the presence of traces of thf it transforms into a monoxide of the ethene adduct with formation of R**Si(μ‐O)(μ‐C 2 H 4 )SiR**. In thf, the disilyne rearranges at r.t. and below by migration of a Si t Bu 3 group with formation of a silyl substituted cyclotrisilene. X‐ray structure determinations of the ethene adduct and its mono‐ and dioxide are presented.