Doubly Stereogenic Sandwich Frameworks: Diastereomeric Metallobiscorroles

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-05-04 DOI:10.1021/acs.inorgchem.5c00598

Kristian Torstensen, Florian Sixt, Abraham B. Alemayehu, Nicholas S. Settineri, Abhik Ghosh

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Abstract

A number of Group 6 metallobiscorrole sandwich compounds with square-antiprismatic coordination were separated into diastereomers by means of careful preparative thin-layer chromatography. The diastereomers differ with respect to the relative orientation of the corrole macrocycles, which are rotated approximately ± 45° or ± 135° relative to each other. The most clear-cut results were obtained for two tungsten corroles, W[TBCF₃PC]₂ {TBCF₃PC = meso-tris[3,5-bis(trifluoromethyl)phenyl]corrolato} and W[TDOMePC]₂ [TDOMePC = meso-tris(3,5-dimethoxyphenyl)corrolato], for which single-crystal X-ray structures were obtained for the 135° diastereomer; the existence of the 45° diastereomer was inferred by elimination and with support from DFT calculations. For Mo[TBCF₃PC]₂ and W[TBCF₃PC]₂, both diastereomers were also fully characterized spectroscopically and their ¹H NMR spectra were essentially fully assigned. The fact that each diastereomer is chiral and exists as two enantiomers (which was previously demonstrated for the 135° form of a tungsten biscorrole) establishes the doubly stereogenic nature of the metallobiscorrole framework – to our knowledge, the first such demonstration for a sandwich compound.

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双立体夹心框架：非对映体金属双微粒

采用制备薄层色谱法，将若干具有方-反柱配位的6族金属双氯夹心化合物分离成非对映体。非对映体的不同之处在于对应大环的相对取向不同，它们彼此相对旋转约为±45°或±135°。对W[TBCF3PC]2 {TBCF3PC =介观三[3,5-二（三氟甲基）苯基]腐蚀}和W[TDOMePC]2 [TDOMePC =介观三[3,5-二甲氧基苯基)腐蚀]这两种钨对映体得到了最明确的结果，它们的135°非对映体得到了单晶x射线结构；45°非对映体的存在是通过消去和DFT计算来推断的。对于Mo[TBCF3PC]2和W[TBCF3PC]2，两种非对映体也进行了完全的光谱表征，其1H NMR谱基本上得到了完全的赋值。事实上，每个非对映体都是手性的，并且以两个对映体的形式存在（这在之前的135°形式的钨双铬化合物中得到了证明），建立了金属双铬框架的双立体性质——据我们所知，这是三明治化合物的第一次这样的证明。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.