Low-temperature C-N and C-O sigma bond homolysis: Recent experimental and computational results.

by McIntosh, Matt

C-N and C-O sigma bond strengths typically fall in the 70-90 kcal/mol range. Thermal homolysis of such bonds would require temps. in excess of 300 °C. When the N or O atom is attached to a highly electron rich alkene, the C-N or C-O homolysis temp. can drop to as low as ambient. We will present historical examples of low temp. (< 100 °C) C-N and C-O sigma bond homolysis as well as recent results from our labs. Computational anal. of the reactions has shed light on the common features of the reactants. Both exptl. and computational results will be discussed.