In Search of the Bailar and Rây-Dutt Twist Mechanisms That Racemize Chiral Trischelates: A Computational Study of ScIII, TiIV, CoIII, ZnII, GaIII
文摘
Two nondissociative processes, a Bailar twist that proceeds through a transition state of D3h symmetry and aRây-Dutt twist mechanism that proceeds through a transition state of C2v symmetry, as well as dissociative/associative processes are potential mechanisms by which the enantiomeric forms of chiral metal trischelates canbe interconverted. We have applied density functional theory to locate the stationary points for metal trischelatesof a -diketonate ligand analogue that interconvert and forms via one or both of these nondissociative pathways.Although many two-dimensional static representations of the Bailar and Rây-Dutt twist mechanisms can be foundin the chemical literature (of the type shown in Figure 1), in this communication, we present our results in the formof interactive three-dimensional animations as a means of enhancing the scientific perception of these fluxionalprocesses.