TY - JOUR
T1 - A retro-Diels Alder route to tetramethyldisilene Me2Si= SiMe2 revisited
T2 - Flow pyrolysis of 1,1,2,2-Tetramethyl-1,2-disilacyclohex-4-ene
AU - Zhou, Dong
AU - Nag, Mrinmoy
AU - Russel, Amber L.
AU - Read, David
AU - Rohrs, Henry W.
AU - Gross, Michael L.
AU - Gaspar, Peter P.
N1 - Funding Information:
We are grateful for financial support from the National Science Foundation and the National Institutes of Health under grants CHE-0316124 and P41RR00954 and to the National Center for Supercomputing Applications, Urbana, IL under grant CHE 84001N and 020027.
PY - 2007/1
Y1 - 2007/1
N2 - Reinvestigation of the flow pyrolysis of 1,1,2,2-tetramethyl-1,2-disilacyclohex-4-ene did not identify conditions under which the retro-Diels Alder reaction was the exclusive process. Extrusion of Me2Si=SiMe2was confirmed, but dimerization of directly extruded Me2Si: contributes significantly to its formation. Rearrangement of 1,1,2,2-tetramethyl-1,2-disilacyclohex-4-ene to 1,1,3,3-tetramethyl-1,3-disilacyclohex-4-ene is a major process under a variety of conditions. Computational studies reduced the number of viable pathways. Both experimental and computational results point to stepwise extrusion of Me2Si=SiMe2 via a diradical intermediate and to linkage by one or more common intermediates of the extrusion pathway and the pathway leading to rearranged disilacyclohexene. Such a mechanism receives support from the formation of 1,2- and 1,3-disilacyclohex-4-enes, that is both the Diels-Alder product and the rearrangement product, in the addition of Me2 Si=SiMe2 to butadiene.
AB - Reinvestigation of the flow pyrolysis of 1,1,2,2-tetramethyl-1,2-disilacyclohex-4-ene did not identify conditions under which the retro-Diels Alder reaction was the exclusive process. Extrusion of Me2Si=SiMe2was confirmed, but dimerization of directly extruded Me2Si: contributes significantly to its formation. Rearrangement of 1,1,2,2-tetramethyl-1,2-disilacyclohex-4-ene to 1,1,3,3-tetramethyl-1,3-disilacyclohex-4-ene is a major process under a variety of conditions. Computational studies reduced the number of viable pathways. Both experimental and computational results point to stepwise extrusion of Me2Si=SiMe2 via a diradical intermediate and to linkage by one or more common intermediates of the extrusion pathway and the pathway leading to rearranged disilacyclohexene. Such a mechanism receives support from the formation of 1,2- and 1,3-disilacyclohex-4-enes, that is both the Diels-Alder product and the rearrangement product, in the addition of Me2 Si=SiMe2 to butadiene.
KW - Chemistry
KW - Computational
KW - Dimethylsilylene
KW - Disila-olefin Diels Alder reaction
KW - Pyrolysis
KW - Reaction mechanism
KW - Tetramethyldisilene
UR - http://www.scopus.com/inward/record.url?scp=33846030172&partnerID=8YFLogxK
U2 - 10.1007/s11201-006-9015-6
DO - 10.1007/s11201-006-9015-6
M3 - Article
AN - SCOPUS:33846030172
VL - 3
SP - 117
EP - 122
JO - Silicon Chemistry
JF - Silicon Chemistry
SN - 1569-0660
IS - 3-4
ER -