Oxidation-dependent Lewis acidity in chalcogen adducts of Sb/P frustrated Lewis pairs†

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2024-06-24 DOI:10.1039/D4DT01591F

Jonas Krieft, Beate Neumann, Hans-Georg Stammler and Norbert W. Mitzel

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Abstract

The reactions of the frustrated Lewis pair (F₅C₂)₂SbCH₂P(tBu)₂ with oxygen, sulphur, selenium and tellurium led to the mono-oxidation products (F₅C₂)₂SbCH₂P(E)(tBu)₂ (E = O, S, Se, Te). Further oxidation of these chalcogen adducts with tetrachloro-ortho-benzoquinone (o-chloranil) gave (F₅C₂)₂Sb(CH₂)(μ-E)P(tBu)₂·Cat^Cl (Cat^Cl = o-O₂C₆Cl₄) with a central four-membered ring heterocycle for E = O, S, and Se. For E = Te the elimination of elemental tellurium led to an oxidation product with two equivalents of o-chloranil, (F₅C₂)₂SbCH₂P(tBu)₂·2Cat^Cl, which is also accessible by reaction of (F₅C₂)₂SbCH₂P(tBu)₂ with o-chloranil. The synthesised compounds were characterised by NMR spectroscopy and X-ray structure analyses, and the structural properties were analysed in the light of the altered Lewis acidity due to the oxidation of the antimony atoms.

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Sb/P 受挫路易斯对的查耳酮加合物中依赖氧化作用的路易斯酸度

受挫路易斯对 (F5C2)2SbCH2P(tBu)2 与氧、硫、硒和碲的反应产生了单氧化产物 (F5C2)2SbCH2P(E)(tBu)2（E = O、S、Se、Te）。这些缩醛加合物与四氯邻苯醌（邻氯苯醌）进一步氧化，得到了 (F5C2)2Sb(CH2)(µ-E)P(tBu)2∙CatCl （CatCl = o-O2C6Cl4），其中 E = O、S、Se 时，中心为四元环杂环。在 E = Te 的情况下，消除碲元素可得到含有两个邻氯苯胺当量的氧化产物 (F5C2)2SbCH2P(tBu)2∙2CatCl，也可通过 (F5C2)2SbCH2P(tBu)2 与邻氯苯胺反应得到。通过核磁共振光谱和 X 射线结构分析对合成的化合物进行了表征，并根据锑原子氧化导致的路易斯酸度改变对其结构特性进行了分析。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.