| For the past several years the Singleton group has been developing a methodology that has greatly enhanced our understanding of reaction pathways. The combination of experimental kinetic isotope effects and ab initio calculations have allowed for an experimental basis for transition state geometries. With the combination of inter- and intramolecular isotope effects, this methodology has been extended to product-determining steps after the rate-determining step. This has allowed us to study a broad range of organic and organometallic catalyzed reactions.;These methods have been applied to the analysis of the Bayer-Villiger oxidation, the ene reaction of singlet oxygen, the Heck reaction, olefin metathesis, the epoxidation of cyclohexenone, and the silane mediated cleavage of carbamates. In developing these new techniques, we were able to propose new mechanisms, different origins of isotope effects, and were able to generate KIEs for several steps of catalytic cycles. |
