Conformational Preferences of Titanocene Dichlorides with Ligands Derived from Menthol: Comparison of Structures in Solution and in the Crystal
Conformational Preferences of Titanocene Dichlorides with Ligands Derived from Menthol: Comparison of Structures in Solution and in the Crystal
复制标题
二茂钛二氯化物与薄荷醇衍生配体的构象偏好：溶液中和晶体中结构的比较
DOI：
10.1021/om0007771
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发表时间：
2001
期刊：
影响因子：
2.8
通讯作者：
M. Keller
中科院分区：
文献类型：
--
作者：
A. Gansäuer;H. Bluhm;Andrés Pierobon;M. Keller
用X射线结晶学和现代核磁共振方法研究了三种含薄荷醇衍生物的化合物1、2和3的结构，确定了它们的固体和溶液结构。在溶液和晶体中，各自的结构基本上是相同的。这种类型的检查似乎还没有出现在文献中。化合物1和2通过环戊二烯基环与薄荷醇取代物相互作用而构象固定。据我们所知，这种远程效应以前从未被观察到，并导致有效的手性转移到手性口袋的远处。研究结果对茂金属催化反应的催化剂设计和类似茂金属化合物的固态和溶液结构测定具有重要意义。
A comparison of the structures of three titanocenes, 1, 2, and 3, with ligands derived from menthol in the solid state and in solution determined by X-ray crystallography and by modern NMR methods has been carried out. The respective structures are essentially the same in solution and in the crystal. It seems that an examination of this type has not appeared in the literature as yet. Complexes 1 and 2 are conformationally fixed by interactions of the cyclopentadienyl ring with the menthol substitutents. This remote effect has to the best of our knowledge not been observed before and leads to efficient chirality transfer to the distant part of the chiral pockets. The results are of relevance for catalyst design in metallocene-catalyzed reactions and for structure determination of similar metallocenes both in the solid state and in solution.