Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5418717 | Journal of Molecular Structure: THEOCHEM | 2007 | 8 Pages |
Abstract
Substituent effects on the reaction profile of the thermal retrocyclization reaction of silacyclobut-2-enes to 1-silabuta-1,3-dienes were studied using B3LYP hybrid density functional theory as well as CCSD and CCSD(T) ab initio calculations. Several different substituents (-CF3, -SiH3, -CN, -OCH3, -OH, and -NH2) were used to investigate their effects on the relative energies of the transition states of the retrocyclization reaction as well as of the 1-silabutadiene products. It was found that Ï-donor groups at the 4-position greatly reduce the energy barriers, and also stabilize the 1-silabutadienes relative to the silacyclobut-2-enes. Silyl substituents at the silicon atom will facilitate the reaction when compared to alkyl substituents. The results thus indicate that the ring-opening reaction of 4,4-disubstituted 1,1-disilylsilacyclobut-2-enes with Ï-donor substituents are particularly suitable entries for formation of 1-silabutadienes of low relative energy.
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Authors
Hui Tong, Anders M. Eklöf, Patrick G. Steel, Henrik Ottosson,