Coordination chemistry of a weakly coordinating carbanion

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2024-11-04 DOI:10.1016/j.poly.2024.117283

Leif Kelling, Viktoria H. Gessner

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Abstract

Carbanions are typically highly reactive species but can be efficiently stabilized to even function as stable weakly coordinating anions (WCA). We now report on the coordination chemistry of the recently introduced allyl anion 1, stabilized by Ar^F (Ar^F = 3,5-bis(trifluoromethyl)phenyl), triflyl substituents, with various s-block metals. A systematic crystallographic study on the s-block metal salts (Li-Cs, Ca) showed that the alkali metals have minimal impact on the anion, as indicated by the similar structural properties compared to the phosphonium salt of 1. In contrast, the calcium complex showed a slightly more pronounced distortion of the allyl symmetry due to stronger Ca–O interactions with the triflyl group. Additionally, the significance of the allyl moiety in stabilizing the carbanionic charge in 1 was demonstrated by comparing the structural parameters and charge distribution with those of an analogous C1-anion. Overall, these studies confirm the enhanced stability of 1 and its weak coordination tendency.

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弱配位碳阴离子的配位化学

烯丙基阴离子通常是高活性物种，但可以被有效地稳定，甚至作为稳定的弱配位阴离子（WCA）发挥作用。我们现在报告的是最近引入的烯丙基阴离子 1 与各种 s-嵌段金属的配位化学反应，烯丙基阴离子 1 通过 ArF（ArF = 3,5-双（三氟甲基）苯基）、三烯丙基取代基稳定。对 s-嵌段金属盐（Li-Cs、Ca）进行的系统晶体学研究表明，碱金属对阴离子的影响微乎其微，这一点从与 1 的鏻盐相似的结构特性中可以看出。相反，钙配合物由于与三烯丙基基团的 Ca-O 相互作用较强，烯丙基对称性发生了略微明显的变形。此外，通过将 1 的结构参数和电荷分布与类似的 C1 阴离子的结构参数和电荷分布进行比较，证明了烯丙基在稳定碳阴离子电荷方面的重要作用。总之，这些研究证实了 1 的稳定性增强及其弱配位倾向。

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

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.