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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Chirality and diastereoselection in the μ-oxo diiron complexes L_2Fe–O–FeL_2(L = bidentate salicylaldiminato)
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Chirality and diastereoselection in the μ-oxo diiron complexes L_2Fe–O–FeL_2(L = bidentate salicylaldiminato)

机译：μ-氧代二铁配合物L_2Fe–O–FeL_2（L =双齿水杨基亚氨基）中的手性和非对映异构

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A number of bis(salicylaldiminato) (Schiff base) complexes of Fe(II)L_2Fe with a variety of ligandsubstituents and functionality are synthesised, usually by salt metathesis but on one occasion via the(sal)_2Fe complex, and characterised by standard methods. Two molecular structure determinationsindicate the expected tetrahedral geometry. Treatment with dry oxygen yielded the Fe(III) complexes[(Fe_2)_2-μ-O], generally in high yield and in the absence of hydroxylated impurities; one bulkycomplex L_2Fe gave no oxidation product for steric reasons, and one hydroxyl-substituted compoundgave an insoluble product. Five molecular structures of these [(FeL_2)_2-μ-O] compounds weredetermined. All were homochiral in the sense that the absolute configuration at Fe was the same forboth atoms. Three of the structures – those based on optically pure salicylaldimine ligands – werediastereomeric. For two, the diastereomers observed are those predicted on the basis of stericconsiderations, while a third highly distorted and congested structure represents the unexpecteddiastereomer. Powder X-ray diffraction confirms high phase purity of the bulk samples (i.e. they arediastereomerically pure to the level detectable). These investigations, coupled with molecular structureand NMR studies on model gallium complexes, indicate that the diastereoselection arises fromcooperative interactions across the oxo bridge
机译：Fe（II）L_2Fe具有许多配体取代基和官能团的许多双（salicylaldiminato）（席夫碱）配合物通常通过盐复分解反应合成，但有时通过（sal）_2Fe配合物进行合成，并通过标准方法进行表征。两种分子结构测定表明预期的四面体几何形状。用干氧处理通常可以高收率且不存在羟基化杂质，生成Fe（III）络合物[（Fe_2）_2-μ-O]。由于空间原因，一种大体积的复合物L_2Fe不产生氧化产物，而一种羟基取代的化合物则给出不溶产物。确定了这些[（FeL_2）_2-μ-O]化合物的五个分子结构。从Fe的绝对构型对于两个原子而言都是相同的意义上讲，它们都是同手性的。其中三个结构-基于光学纯的水杨醛亚胺配体的结构-非对映异构体。对于两个，观察到的非对映异构体是根据空间构想预测的非对映异构体，而第三个高度扭曲和拥塞的结构则代表了意外的非对映异构体。粉末X射线衍射证实了大块样品的高相纯度（即它们是非对映体纯的，可检测到的水平）。这些研究，以及对模型镓配合物的分子结构和NMR研究表明，非对映选择是由跨氧代桥的合作相互作用引起的。

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