| This dissertation comprises two main research projects. The first project, presented in Chapter 1, involves the synthesis and thermochemistry of germacyclobutanes (germetanes). Four new germetanes (spirodigermetane, diallylgermetane, dichlorogermetane, and germacyclobutane) have been synthesized using a modified di-Grignard synthesis. Diallylgermetane is shown to be a useful starting material for obtaining other germetanes, particularly the parent germetane, germacyclobutane. The gas-phase thermochemistries of spirodigermetane, diallylgermetane and germacyclobutane have been explored via pulsed stirred-flow reactor (SFR) studies, showing remarkable differences in decomposition, depending on the substitution at the germanium atom.; The second project investigates the thermochemical, photochemical, and catalytic additions of several digermanes to acetylenes. The first examples of thermo- and photochemical additions of Ge-Ge bonds to C≡C are demonstrated. Mechanistic investigations are described and comparisons are made to analogous disilane addition reactions, previously studied in our group. |
