Isomerization of Silylallene

The isomerization of silylallene to seven of its isomers has been studied using ab initio molecular orbital theory. The energetics were obtained using quadratically convergent configuration interaction (QCISD(T)) with the 6-311G(d,p) basis set, at geometries optimized by second-order perturbation theory (MP2) with the 6-31G(d) basis set. Test calculations using multiconfiguration wave functions show that the configurational mixing is small; therefore, the single-configuration-based methods are reliable. In comparison to the isomerization of the parent allene, the silyl group was found to migrate more easily than the hydrogen. In particular, the 1,3-migration that converts silylallene to silylpropyne has barriers of 55.8 and 52.9 kcal mol-1 for the forward and backward reactions, respectively. These are roughly half of the 1,3-hydrogen migration barrier in allene. Disciplines Chemistry Comments Reprinted (adapted) with permission from Organometallics 14 (1005): 3827, doi:10.1021/om00008a033. Copyright 1995 American Chemical Society. This article is available at Iowa State University Digital Repository: http://lib.dr.iastate.edu/chem_pubs/298 Organometallics 1995, 14, 3827-3831 3827 Isomerization of Silylallene Hideaki Shimizut and MarkS. Gordon* Department of Chemistry, Iowa State University, Ames, Iowa 50011 Received March 31, 1995° The isomerization of silylallene to seven of its isomers has been studied using ab initio molecular orbital theory. The energetics were obtained using quadratically convergent configuration interaction (QCISD(T)) with the 6-311G(d,p) basis set, at geometries optimized by second-order perturbation theory (MP2) with the 6-31G(d) basis set. Test calculations using multiconfiguration wave functions show that the configurational mixing is small; therefore, the single-configuration-based methods are reliable. In comparison to the isomerization of the parent allene, the silyl group was found to migrate more easily than the hydrogen. In particular, the 1,3-migration that converts silylallene to silylpropyne has barriers of 55.8 and 52.9 kcal mol1 for the forward and backward reactions, respectively. These are roughly half of the 1,3-hydrogen migration barrier in allene.