Abstract
Ab initio RHF/6-31G* and MP2-fc/6-31G* computations predict that a very shallow local minimum of the LiNH2·OCHMe dimer exists in which the carbonyl oxygens adopt the bridging role, and further that the activation enthalpy of acetaldehyde enolization by LiNH2 is significantly lower for such a dimeric intermediate than for an unsolvated monomeric intermediate. Solvation of the monomeric intermediate with dimethyl ether reduces the activation enthalpy of enolization, but not to the near-zero level found for the bridged carbonyl dimer. However, starting from the amide-bridged dimeric global minimum, the solvated monomeric local minimum from which the transition state evolves is more easily accessible than the carbonyl-bridged dimeric local minimum. Inclusion of electron correlation effects is imperative in the determination of the transition state barriers.
| Original language | English |
|---|---|
| Pages (from-to) | 262-267 |
| Number of pages | 5 |
| Journal | New Journal of Chemistry |
| Volume | 25 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - 2001 |
Keywords
- Carbonyl group (bridging; proton transfer via dimer intermediate with bridging carbonyl groups in amidolithium-mediated enolization); Dimers Role: FMU (Formation, unclassified), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), FORM (Formation, nonpreparative), PROC (Process), RACT (Reactant or reagent) (mechanistic reaction intermediate; proton transfer via dimer intermediate with bridging carbonyl groups in amidolithium-mediated enolization); Molecular structure (optimized; proton transfer via dimer intermediate with bridging carbonyl groups in amidolithium-mediated enolization); Ab initio methods; Activation energy; Activation enthalpy; Basis sets; Electron correlation; Enolization; MP2; Molecular orientation; Potential barrier; Potential energy hypersurface; Proton transfer; RHF; Solvation; Total energy; Transition state structure; Vibrational frequency (proton transfer via dimer intermediate with bridging carbonyl groups in amidolithium-mediated enolization)