Theoretical calculations on the tetramethyldisilene rearrangement: a new approach to an old mechanistic problem.
Roark and Peddle first observed that, when not trapped, Me(2)Si=SiMe(2) underwent a series of rearrangements to give two major isomeric products: 1,1-dimethyl-1,3-disilacyclobutane and 1,3-dimethyl-1,3-disilacyclobutane. The widely accepted mechanism for this rearrangement was proposed by Barton and co-workers. However, little is known about the thermodynamic or kinetic properties of this reaction, because the relevant data are limited to the product ratios of the two isomers. Our calculations predict that the product ratio is driven by kinetic control rather than thermodynamic control. We also show that new DFT functionals, such as MPW1K and M052X, produce thermochemical results comparable with CCSD(T) calculations.
Nag
Mrinmoy
M
Department of Chemistry, Washington University, St. Louis, MO 63130-4899 (USA), Fax: (+1) 314-935-4481.
Gaspar
Peter P
PP
Department of Chemistry, Washington University, St. Louis, MO 63130-4899 (USA), Fax: (+1) 314-935-4481.