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ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 2013,Vol.29>> Issue(06)>> 1183-1191     doi: 10.3866/PKU.WHXB201304122         中文摘要
THERMODYNAMICS, KINETICS, AND STRUCTURAL CHEMISTRY
Mirror Symmetry Breaking and Absolute Configuration Correlations of Fe(III) Complexes with Achiral Substituted o-Iminobenzosemiquinonato Ligands
ZHAO Lei, WAN Shi-Gang, CHEN Cheng-Dong, LIN Yi-Ji, FANG Xue-Ming, ZHANG Hui
State Key Laboratory of Physical Chemistry of Solid Surface, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
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A pair of chiral o-iminobenzosemiquinonato Fe(III) complexes, Λ-mer- [Fe(LISQ)3] and Δ-mer-[Fe(LISQ)3] (LISQ: 2-phenylimino-4, 6-di-tert-butylphenol, mer: meridian configuration), were synthesized from 2-anilino-4,6-di-tert-butylphenol (H2L) and FeCl2·4H2O. Their absolute configurations were determined by single crystal X-ray diffraction (XRD) and solid-state circular dichroism (CD) spectra (the same single crystal for XRD was dispersed in KCl). Correlations between the absolute configurations of the chiral-atmetal o-iminobenzosemiquinonato M(III) complexes [M(LISQ)3] (M=Cr, Fe, Co) and their solid-state CD spectra were also established. Comparison between solid-state CD spectra of the bulk samples from 10 different syntheses and their single crystals were thoroughly analyzed. The solid-state CD spectra of the powdered samples from 10 different crystallizations of one product were characterized. These studies indicated that mirror symmetry breaking (MSB) occurred during the crystallization process of the Fe(III) complexes and their enantiomeric excess (ee) values were between 15% and 100%.



Keywords: Semiquinone Fe(III) complexes   Mirror symmetry breaking   Absolute configuration   Solid-state CD spectroscopy   Single crystal X-ray diffraction  
Received: 2013-01-25 Accepted: 2013-04-09 Publication Date (Web): 2013-04-12
Corresponding Authors: Email: huizhang@xmu.edu.cn

Fund: The project was supported by the National Natural Science Foundation of China (21273175, 20973136).

Cite this article: ZHAO Lei, WAN Shi-Gang, CHEN Cheng-Dong, LIN Yi-Ji, FANG Xue-Ming, ZHANG Hui. Mirror Symmetry Breaking and Absolute Configuration Correlations of Fe(III) Complexes with Achiral Substituted o-Iminobenzosemiquinonato Ligands[J]. Acta Phys. -Chim. Sin., 2013,29 (06): 1183-1191.    doi: 10.3866/PKU.WHXB201304122

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