Electronic Thesis and Dissertation Repository


Master of Science




Baines, Kim M.


The mechanism for the addition of alkynes to low-valent silicon compounds was investigated in this thesis using a cyclopropyl alkyne mechanistic probe (1.31). The addition of alkyne 1.31 to the asymmetrically-substituted disilene 1.37 was investigated. The structures of the products obtained indicate the reaction proceeds through a stepwise mechanism with a biradical intermediate and the dipole moment of the disilene bond was not sufficient to alter the reaction mechanism.

The addition of alkyne 1.31 to the NHC-stabilized silylene 1.38 was also investigated. The structure of the product formed in the reaction lead to two conclusions: that silylene 1.38 acts as a nucleophile in the reaction with alkyne 1.31, and the cyclopropyl ring of alkyne 1.31 regioselectively opens toward the phenyl substituent in the presence of an α-anion.