Molecular modeling studies of the intramolecular twist mechanisms of racemization for tris chelate complexes

The preferred mechanisms of racemization for three tris chelate complexes, Co(acac)₃, Fe(phen)₃ ³⁺ and FeS₂CN(CH₂)₄]₃, were investigated by molecular modeling. The transition states for both a Bailar twist and a Rây-Dutt twist were considered; semi-empirical calculations (PM3) yielded activation energies. The preferred mechanism was the Bailar twist for Co(acac)₃ and FeS₂CN(CH₂)₄]₃ with activation energies of 83.2 and 7.3 kcal mol⁻¹, respectively, and the Rây-Dutt twist for Fe(phen)₃ ³⁺ with an activation energy of 114.4 kcal mol⁻¹. These results are compared with those of geometrical models.