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Fe(CO) 阴离子的自发分解以及手性客体分子在 BEDT-TTF 自由基阳离子盐中的包合

Spontaneous Resolution of the Fe(CO) Anion and Inclusion of Chiral Guest Molecules in BEDT-TTF Radical-Cation Salts.

作者信息

Ogar Joseph O, Wallis John D, Blundell Toby J, Rusbridge Elizabeth K, Mantle Alex, Akutsu Hiroki, Nakazawa Yasuhiro, Imajo Shusaku, Martin Lee

机构信息

School of Science and Technology, Nottingham Trent University, Nottingham, Clifton Lane NG11 8NS, U.K.

Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan.

出版信息

Inorg Chem. 2025 Jan 20;64(2):1075-1084. doi: 10.1021/acs.inorgchem.4c04622. Epub 2025 Jan 6.

DOI:10.1021/acs.inorgchem.4c04622
PMID:39763286
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11752079/
Abstract

We report the synthesis of three radical-cation salts of BEDT-TTF from racemic tris(oxalato)ferrate by electrocrystallization in the presence of chiral molecules. In the presence of enantiopure l-(+)-tartaric acid, we observe spontaneous resolution of the labile tris(oxalato)ferrate anion to produce the chiral radical-cation salt α-(BEDT-TTF)[Δ-Fe(CO)].[l-(+)-tartaric acid] which contains only the Δ enantiomer of Fe(CO). Using enantiopure ()-(-)-3-hydroxytetrahydrofuran as an additive gives α-(BEDT-TTF)[Fe(oxalate)].(HO).ethanol.()-(-)-3-hydroxytetrahydrofuran, which includes the chiral guest and contains a racemic mixture of Λ and Δ enantiomers of Fe(CO). Enantiopure ()-phenyloxirane is hydrolyzed to racemic 1-phenylethane-1,2-diol to produce racemic β"-β"-(BEDT-TTF)(HO/HO)Fe(CO).1-phenylethane-1,2-diol.

摘要

我们报道了在手性分子存在下，通过电结晶由外消旋三（草酸根）铁酸盐合成三种BEDT-TTF自由基阳离子盐。在对映体纯的L-(+)-酒石酸存在下，我们观察到不稳定的三（草酸根）铁酸根阴离子自发拆分，生成手性自由基阳离子盐α-(BEDT-TTF)[Δ-Fe(CO)].[L-(+)-酒石酸]，其仅含有Fe(CO)的Δ对映体。使用对映体纯的()-(-)-3-羟基四氢呋喃作为添加剂得到α-(BEDT-TTF)[Fe(草酸盐)].(HO).乙醇.()-(-)-3-羟基四氢呋喃，其包含手性客体且含有Fe(CO)的Λ和Δ对映体的外消旋混合物。对映体纯的()-苯基环氧乙烷水解为外消旋1-苯基乙烷-1,2-二醇，以生成外消旋β"-β"-(BEDT-TTF)(HO/HO)Fe(CO).1-苯基乙烷-1,2-二醇。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eeab/11752079/6cc60e83d1a4/ic4c04622_0017.jpg
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