低配位膦正离子化合物的研究进展

doi:10.6023/cjoc202502021

摘要/Abstract

近10年对低配位主族元素化合物(如硅卡宾和锗卡宾)的研究表明, 它们具有类似于过渡金属的催化反应性质. 膦正离子是二价磷衍生物, 结构中含有空位3p轨道与孤对电子, 具有高度的反应性. 稳定膦正离子的方式可分为热力学稳定法与动力学稳定法. 热力学稳定法通过电子对膦正离子空位3p轨道的配位完成. 具有大空间位阻的取代基同样可以保护膦正离子的空位3p轨道, 从而实现动力学稳定. 膦正离子通常由膦卤前体化合物与强亲电卤代试剂反应制备. 膦正离子同时具有Lewis酸与Lewis碱的化学性质. 近年来, 基于二茂铁骨架的杂原子取代膦正离子由于具有优异的氧化还原性质受到研究者的关注, 然而此类化合物的前线轨道主要位于二茂铁基团的铁原子上, 表明磷中心并未参与氧化还原反应. 文章从研究化合物氧化还原行为的角度指出, 被大位阻二茂铁基团取代的膦正离子不仅可以实现动力学稳定, 具有优异的氧化还原活性, 其前线轨道也位于磷原子上. 设计并合成具有稳定氧化还原行为、高反应活性、动力学稳定的膦正离子将为此领域的研究趋势.

关键词: 低配位主族化合物, 膦正离子, 动力学稳定法, 氧化还原性质, 二茂铁基团

Recent studies on the low-coordinate species of the heavier main group elements, such as silylenes and germylenes, have shown that they can behave similarly to the transition metal complexes. Phosphenium ions, derivatives of divalent phosphorus which have both vacant 3p-orbital and lone pair electrons, are intrinsically highly reactive. The stabilization methods of phosphenium ions can be categorized into thermodynamic and kinetic stabilization. Thermodynamic stabilization is achieved by coordinating electrons with 3p-orbitals of phosphenium ions. Moreover, 3p-orbitals of phosphenium ions can be kinetically stabilized by steric protection with bulky substituents. So far, the most widely used synthetic method for phosphenium ions is the halogen abstraction from the neutral halophosphine precursor, which can be accomplished by strongly electrophilic halide scavengers. Phosphenium ions exhibit both Lewis acid and Lewis base chemical properties. In recent years, nitrogen-substituted phosphenium ions based on the ferrocenyl frameworks have attracted substantial attention due to their stable redox behavior. However, since the highest occupied molecular orbital (HOMO) of such species is predominantly located on the iron atom of ferrocenyl group, it is considered that the central phosphorus atom is not involved in the redox process. From the perspective of studying the redox behavior of phosphenium ions, the review indicates that phosphenium ions with bulky ferrocenyl groups can be kinetically stabilized and the frontier orbitals can be located on the central phosphorus atom. The design and synthesis of phosphenium ions with stable redox behavior, high reactivity, and kinetic stability will become the research trend in this field.

Key words: low-coordinate main group species, phosphenium ions, kinetic stabilization, redox behavior, ferrocenyl group

引用此文

张天庆, 吴修明, 王丛丛. 低配位膦正离子化合物的研究进展[J]. 有机化学, 2025, 45(9): 3244-3254.

Tianqing Zhang, Xiuming Wu, Congcong Wang. Research Progress of Low-Coordinate Phosphenium Ions Compounds[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3244-3254.

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图/表 13

图式1. 过渡金属催化剂应用于交叉偶联反应

Scheme 1. Application of transition metal catalysts in cross coupling reactions

图式2. 过渡金属催化剂应用于交叉偶联反应

Scheme 2. Application of transition metal catalysts in cross coupling reactions

图式3. 膦正离子的结构

Scheme 3. Structure of phosphenium ions

图式4. 膦正离子的热力学稳定法与动力学稳定法

Scheme 4. Thermodynamic and kinetic stabilization of phosphenium ions

图式5. 热力学稳定策略合成的膦正离子实例

Scheme 5. Selected examples of isolable phosphenium ions stabilized by thermodynamic effects

图式6. 动力学稳定策略合成的膦正离子实例

Scheme 6. The examples of isolable phosphenium ion stabilized by kinetic effects

图式7. 膦正离子的常见合成策略

Scheme 7. Some common synthetic strategies of phosphenium ions

图式8. 膦正离子的常见反应

Scheme 8. Some common reactions of phosphenium ions

图式9. 膦正离子配合物的反应性质

Scheme 9. Some common reactions of phosphenium ions

图式10. 含二茂铁基的硅烯与其氧化还原性质

Scheme 10. Redox behavior of ferrocenyl-substituted disilene

图式11. 基于二茂铁骨架的低配位主族元素化合物的HOMO

Scheme 11. HOMO of low-coordinate main group elements species based on ferrocenyl frameworks

图式12. 具有大空间位阻二茂铁取代基膦正离子的氧化还原性质

Scheme 12. Redox behavior of phosphenium ion based on sterically demanding ferrocenyl groups

图式13. 膦正离子催化反应实例

Scheme 13. Examples of reaction catalyzed by phosphenium ions

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