Synthesis and Stabilization of Highly Reactive Haloacetylium Ions.

IF 3.3 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry Pub Date : 2024-09-23 DOI:10.1021/acs.joc.4c01783

Sebastian Steiner, Christoph Jessen, Alexander Nitzer, Valentin Bockmair, Andreas J Kornath

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引用次数: 0

Abstract

The reactions of selected haloacetyl fluorides with the strong Lewis acids AsF₅ and SbF₅ were investigated in the aprotic solvent SO₂ClF. Depending on the stoichiometric ratio of AsF₅ or SbF₅ and the haloacetyl fluorides, either O-coordinated adducts or the respective haloacetylium ions were isolated as solids. The compounds were characterized by low-temperature vibrational spectroscopy and single-crystal X-ray diffraction. [CClH₂CO][Sb₂F₁₁] and [CH₂FCO][Sb₂F₁₁] crystallize in the monoclinic space group P2₁ with two formula units per unit cell. The reactivity of the haloacetyl fluorides under Lewis acidic conditions is discussed based on quantum chemical calculations of fluoride ion affinities on the BP/def2SVPP level of theory. The haloacetylium ions are stabilized in the solid-state phase by intermolecular C···F contacts and electron donation of the fluorine ligands of the anions as well as intramolecular hyperconjugation.

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高活性卤乙酰离子的合成与稳定。

研究人员在无相溶剂 SO2ClF 中研究了某些卤乙酰氟化物与强路易斯酸 AsF5 和 SbF5 的反应。根据 AsF5 或 SbF5 与卤乙酰氟化物的化学计量比，可以分离出 O 配位加合物或相应的卤乙酰基离子固体。通过低温振动光谱和单晶 X 射线衍射对这些化合物进行了表征。[CClH2CO][Sb2F11]和[CH2FCO][Sb2F11]在单斜空间群 P21 中结晶，每个单胞有两个式单元。根据 BP/def2SVPP 理论水平上氟离子亲和力的量子化学计算，讨论了卤乙酰氟化物在路易斯酸条件下的反应性。卤乙酰鎓离子在固态阶段通过分子间的 C-F 接触、阴离子的氟配体的电子捐赠以及分子内的超共轭作用而得到稳定。

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

The Journal of Organic Chemistry 化学-有机化学

CiteScore

6.20

自引率

11.10%

发文量

1467

审稿时长

2 months

期刊介绍： The Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.