Stable Silenolates and Brook-Type Silenes with Exocyclic Structures.
The first silenolates with exocyclic structures [(Me3Si)2Si(Si2Me4)2SiC(R)O]-K+(2a: R = 1-adamantyl;2b: mesityl;2c:o-tolyl) were synthesized by the reaction of the corresponding acylcyclohexasilanes1a-cwith KOtBu. NMR spectroscopy and single-crystal X-ray diffraction analysis suggest that the aryl-substituted silenolates2b,cexhibit increased character of functionalized silenes as compared to the alkyl-substituted derivative2adue to the different coordination of the K+counterion to the SiC(R)O moiety.2b,c, thus, reacted with ClSiiPr3to give the exocyclic silenes (Me3Si)2Si(Si2Me4)2Si=C(OSiiPr3)R (3b: R = Mes;3c:o-Tol), while2aafforded the Si-silylated acylcyclohexasilane1d. The thermally remarkably stable compound3b, which is the first isolated silene with the sp2silicon atom incorporated into a cyclopolysilane framework, could be fully characterized structurally and spectroscopically.
Institute of Inorganic Chemistry and Institute for Chemistry and Technology of Materials, Graz University of Technology , Stremayrgasse 9, A-8010 Graz, Austria.
Michael
M
Haas
Institute of Inorganic Chemistry and Institute for Chemistry and Technology of Materials, Graz University of Technology , Stremayrgasse 9, A-8010 Graz, Austria.
Roland
R
Fischer
Institute of Inorganic Chemistry and Institute for Chemistry and Technology of Materials, Graz University of Technology , Stremayrgasse 9, A-8010 Graz, Austria.
Michaela
M
Flock
Institute of Inorganic Chemistry and Institute for Chemistry and Technology of Materials, Graz University of Technology , Stremayrgasse 9, A-8010 Graz, Austria.
Stefan
S
Mueller
Institute of Inorganic Chemistry and Institute for Chemistry and Technology of Materials, Graz University of Technology , Stremayrgasse 9, A-8010 Graz, Austria.
Martin
M
Rausch
Institute of Inorganic Chemistry and Institute for Chemistry and Technology of Materials, Graz University of Technology , Stremayrgasse 9, A-8010 Graz, Austria.
Robert
R
Saf
Institute of Inorganic Chemistry and Institute for Chemistry and Technology of Materials, Graz University of Technology , Stremayrgasse 9, A-8010 Graz, Austria.
Ana
A
Torvisco
Institute of Inorganic Chemistry and Institute for Chemistry and Technology of Materials, Graz University of Technology , Stremayrgasse 9, A-8010 Graz, Austria.
Harald
H
Stueger