使用中性和阴离子衍生化环糊精对钌（II）三二亚胺配合物进行对映选择性主客体络合作用。
Enantioselective Host-Guest Complexation of Ru(II) trisdiimine complexes using neutral and anionic derivatized cyclodextrins.
作者信息
Sun Ping, Macdonnell Frederick M, Armstrong Daniel W
机构信息
Department of Chemistry and Biochemistry, The University of Texas at Arlington, TX 76019, USA.
出版信息
Inorganica Chim Acta. 2009 Jul 1;362(9):3073-3078. doi: 10.1016/j.ica.2009.02.003.
Enantioselective host-guest complexation between five racemic Ru(II) trisdiimine complexes and eight derivatized cyclodextrins (CDs) has been examined by NMR techniques. The appearance of non-equivalent complexation-induced shifts of between the Δ and Λ-enantionomers of the Ru(II) trisdiimine complexes and derivatized CDs is readily observed by NMR. In particular, sulfobutyl ether-β-cyclodextrin sodium salt (SBE-β-CD), R-naphtylethyl carbamate β-cyclodextrin (RN-β-CD), and S-naphtylethyl carbamate β-cyclodextrin (SN-β-CD) showed good enantiodiscrimination for all five Ru complexes examined, which indicates that aromatic and anionic derivatizing groups are beneficial for chiral recognition. The complexation stoichiometry between SBE-β-CD and Ru(phen)(3) was found to be 1: 1 and binding constants reveal that Λ-Ru(phen)(3) binds more strongly to SBE-β-CD than the Δ-enantiomer. Correlations between this NMR method and separative techniques based on CDs as chiral discriminating agents (i.e., selectors) are discussed in detail.
通过核磁共振技术研究了五种外消旋钌（II）三二亚胺配合物与八种衍生化环糊精（CDs）之间的对映选择性主客体络合作用。通过核磁共振很容易观察到钌（II）三二亚胺配合物和衍生化环糊精的Δ和Λ对映体之间出现非等效的络合诱导位移。特别是，磺丁基醚-β-环糊精钠盐（SBE-β-CD）、R-萘基乙基氨基甲酸酯β-环糊精（RN-β-CD）和S-萘基乙基氨基甲酸酯β-环糊精（SN-β-CD）对所研究的所有五种钌配合物都表现出良好的数据歧视，这表明芳香族和阴离子衍生基团有利于手性识别。发现SBE-β-CD与[Ru（phen）（3）]（2+）之间的络合化学计量比为1:1，结合常数表明Λ-[Ru（phen）（3）]（2+）与SBE-β-CD的结合比Δ对映体更强。详细讨论了这种核磁共振方法与基于环糊精作为手性鉴别剂（即选择剂）的分离技术之间的相关性。
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