A Retro-Diels Alder route to Tetramethyldisilene Me2Si=SiMe2 revisited: Flow Pyrolysis of 1,1,2,2-Tetramethyl-1,2-disilacyclohex-4-ene
作者： Dong Zhou , Mrinmoy Nag , Amber L. Russel , David Read , Henry W. Rohrs
DOI: 10.1007/S11201-006-9015-6
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摘要: Reinvestigation of the flow pyrolysis 1,1,2,2-tetramethyl-1,2-disilacyclohex-4-ene did not identify conditions under which retro-Diels Alder reaction was exclusive process. Extrusion Me2Si=SiMe2was confirmed, but dimerization directly extruded Me2Si: contributes significantly to its formation. Rearrangement 1,1,3,3-tetramethyl-1,3-disilacyclohex-4-ene is a major process variety conditions. Computational studies reduced number viable pathways. Both experimental and computational results point stepwise extrusion Me2Si=SiMe2 via diradical intermediate linkage by one or more common intermediates pathway leading rearranged disilacyclohexene. Such mechanism receives support from formation 1,2- 1,3-disilacyclohex-4-enes, that both Diels-Alder product rearrangement product, in addition butadiene.
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