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The Metal as Source of Chirality in Octahedral Complexes with Tripodal Tetradentate Ligands
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-01-10 , DOI: 10.1021/jacs.7b12731
María Carmona 1 , Ricardo Rodríguez 1 , Vincenzo Passarelli 1, 2 , Fernando J. Lahoz 1 , Pilar García-Orduña 1 , Daniel Carmona 1
Affiliation  

The challenging control of the absolute configuration of chiral-at-metal complexes is efficiently achieved using the tripodal tetradentate ligand L. The optical resolution of rac-[RhCl2(κ4C,N,N',P-L)] mediated by (S)-α-phenylglycine provides access to enantiopure complexes of general formula [Rh(κ4C,N,N',P-L)A(Solv)][SbF6]n that enantioselectively catalyze the Diels-Alder reaction between methacrolein and HCp with enantiomeric ratio of up to >99/1. The nature of the active species, the origin of the enantioselectivity and mechanistic details are disclosed by means of NMR spectroscopy and DFT studies.

中文翻译:

金属作为三足四齿配体八面体配合物中手性的来源

使用三足四齿配体 L 有效地实现了手性金属配合物绝对构型的挑战性控制。 (S)-α 介导的 rac-[RhCl2(κ4C,N,N',PL)] 的光学分辨率-苯基甘氨酸提供通式 [Rh(κ4C,N,N',PL)A(Solv)][SbF6]n 的对映体纯复合物,其对映选择性催化异丁烯醛和 HCp 之间的 Diels-Alder 反应,对映体比例高达 > 99/1。活性物质的性质、对映选择性的起源和机械细节通过 NMR 光谱和 DFT 研究公开。
更新日期:2018-01-10
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