In Search of the Bailar and Rây-Dutt Twist Mechanisms That Racemize Chiral Trischelates: A Computational Study of ScIII, TiIV, CoIII, ZnII, GaIII
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- 作者：Henry S. Rzepa ; Marion E. Cass
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：September 17, 2007
- 年：2007
- 卷：46
- 期：19
- 页码：8024 - 8031
- 全文大小：346K
- 年卷期：v.46,no.19(September 17, 2007)
- ISSN：1520-510X
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.