Issue 18, 2010
From the journal:

Dalton Transactions

Chiral resolution of a racemic macrocyclic complex by recognition of one enantiomer over the other: structures and DFT calculations†

Guang-Chuan Ou,ab   Zi-Zhou Wang,a   Li-Zi Yang,a   Cun-Yuan Zhaoa  and  Tong-Bu Lu*a  

* Corresponding authors

a MOE Key Laboratory of Bioinorganic and Synthetic Chemistry/State Key Laboratory of Optoelectronic Materials and Technologies/School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, China
E-mail: lutongbu@mail.sysu.edu.cn
Tel: +86-20-84112921

b Department of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou, Hunan, China

Abstract

The enantiopure agents d- and l-leucine, selectively bind RR and SS enantiomers from a racemate [Ni(α-rac-L)]2+ to give {[Ni(RR-L)(d-HLeu)](ClO4)2}n (Δ-1) and {[Ni(SS-L)(l-HLeu)](ClO4)2}n (Λ-1), respectively, and leave the corresponding uninteracted SS and RR enantiomers of [Ni(α-SS-L)](ClO4)2 (S-2) and [Ni(α-RR-L)](ClO4)2 (R-2). Occasionally, a few crystals of {[Ni(RR-L)(l-HLeu)](ClO4)2}n (Δ-3) and {[Ni(SS-L)(d-HLeu)](ClO4)2}n (Λ-3) were found to have accreted with the crystals of Λ-1/R-2, and Δ-1/S-2, respectively (the yields are less than 2%). The results of X-ray crystal structural analysis reveal that Δ-1 and Λ-1, S-2 and R-2, and Δ-3 and Λ-3 are enantiomers, in which Δ-1 and Δ-3 possess 1D right-handed helical chains, while Λ-1 and Λ-3 exhibit a motif of 1D left-handed helical chains. The results of DFT calculations reveal that the single-point energies of [Ni(RR-L)(d-HLeu)]2+/[Ni(SS-L)(l-HLeu)]2+ in Δ-1/Λ-1 are 582 kJ mol−1 lower than those of [Ni(RR-L)(l-HLeu)]2+/[Ni(SS-L)(d-HLeu)]2+ in Δ-3/Λ-3, demonstrating the favorable stereo-coordination environments of [Ni(α-RR-L)]2+ and [Ni(α-SS-L)]2+ towards d and l-HLeu, respectively.

Graphical abstract: Chiral resolution of a racemic macrocyclic complex by recognition of one enantiomer over the other: structures and DFT calculations

About
Cited by
Related
Download options Please wait...

Supplementary files

Article information

DOI
https://doi.org/10.1039/B921141A
Article type
Paper
Submitted
12 Oct 2009
Accepted
10 Mar 2010
First published
24 Mar 2010

Dalton Trans., 2010,39, 4274-4279

Permissions

Request permissions

Chiral resolution of a racemic macrocyclic complex by recognition of one enantiomer over the other: structures and DFT calculations

G. Ou, Z. Wang, L. Yang, C. Zhao and T. Lu, Dalton Trans., 2010, 39, 4274 DOI: 10.1039/B921141A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements