A Computational Investigation of the Retrocyclization Reaction of Silacyclo-but-2-enes to 1-silabuta-1,3-dienes: Focus on the effect of the substituents
2007 (English)In: Journal of Molecular Structure: THEOCHEM, ISSN 0166-1280, Vol. 811, no 1-3, 153-160 p.Article in journal (Refereed) Published
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 π-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 π-donor substituents are particularly suitable entries for formation of 1-silabutadienes of low relative energy.
Place, publisher, year, edition, pages
2007. Vol. 811, no 1-3, 153-160 p.
Silicon, Retrocyclization, Density functional theory, Ab initio, Silene, Silacyclobut-2-ene, 1-Silabutadiene
IdentifiersURN: urn:nbn:se:uu:diva-97588DOI: 10.1016/j.theochem.2007.02.024ISI: 000247053500018OAI: oai:DiVA.org:uu-97588DiVA: diva2:172588