The gas phase reactions between Cu+ and 2-propanol have been investigated using density functional theory at the B3LYP/6-311++G(d) and B3LYP/6-311++G(d,p) levels of theories. Seven reaction pathways have been studied. Of all reaction paths, the mechanism involving an electrophile-induced one step syn elimination of H2O has the lowest energy barrier. Dehydration also occurs via the intermediate corresponding to C-O insertion of Cu+. On the H2 elimination channel, reaction begins with C-H insertion of Cu+, followed by hydrogen migrations to form H2-Cu+-acetone or the H2-Cu+-2-propenol intermediates. Our results show that the reaction with copper cation insertion into the H-OCH(CH3)2 bond is unlikely, for its activation energy is 24.5 kcal/mol higher than those of the reactants (Cu+ and 2-propanol). The mechanism involving C-C insertion of Cu+ is also energetically unfavorable. The predicted potential energy surface of reaction and relative energies of the fragmentation products are consistent with available gas phase experiments.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry