Thermodynamics and Kinetics of Glyoxal Dimer Formation: A Computational Study

• DOI: 10.1021/jp076573g
• Publication Date: 2007-12-08T09:00:26Z
• Authors: Jeremy Kua; Sean W. Hanley; David O. De Haan
• Keywords: Glyoxal; Trimer; Dioxolane

Density functional theory (B3LYP//6-311+G*) calculations including Poisson−Boltzmann implicit solvent were used to study the hydration of glyoxal and subsequent formation dimeric species in solution. Our show that dioxolane ring dimer is thermodynamic sink among all monomers dimers with varying degrees hydration. Although fully hydrated are thermodynamically favored over their less counterparts, we find a preliminary dehydration step precedes dimerization closure. Ring closure open monohydrate kinetically both dihydrate form dioxane dimer. The kinetic barriers for different geometric approaches suggest an explanation why oligomerization stops after trimer as observed experimentally.