Stereoisomerism in bridged octahedral dimeric complexes with tetradentate ligands. Diastereospecific formation of syn-delta delta-(cis-beta-L)TiO2 (L-chiral salen type ligands)

Enantiomer Pub Date : 2000-01-01
Tararov, Larichev, Moscalenko, Yashkina, Khrustalev, Antipin, Borner, Belokon
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Abstract

The first two examples of the successful application of chiral salen ligands for diastereoselective syntheses of dinuclear Ti(IV), (L1Ti)2O2 and (PdI2L2Ti)2O2 species with defined chirality and geometry at the metal centre are presented. The structure of the complexes was established by X-ray structural analysis. Both complexes have similar structural features: (1) chiral salen ligands have cis-beta configuration around Ti centres, (2) (R,R) chirality of ligands induces delta helicity of ligand, and (3) syn arrangement of ligand donor atoms in relation to the TiO2Ti plane. Stereoselective effects of the dimers are discussed engaging available literature data. A model has been proposed to rationalise high syn selectivity in the formation of dimers.

带有四齿配体的桥接八面体二聚体配合物的立体异构。顺式-(顺式- β - l)TiO2 (l -手性salen型配体)的非对映特异性形成
本文介绍了手性salen配体在非对映选择性合成双核Ti(IV), (L1Ti)2O2和(PdI2L2Ti)2O2的前两个例子,它们具有明确的手性和金属中心的几何形状。通过x射线结构分析确定了配合物的结构。这两种配合物具有相似的结构特征:(1)手性salen配体在Ti中心周围具有顺式β构型;(2)配体的(R,R)手性诱导配体的δ螺旋;(3)配体供体原子相对于TiO2Ti平面的同步排列。利用现有文献资料讨论了二聚体的立体选择性效应。提出了一个模型来解释二聚体形成过程中的高syn选择性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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