从有机胺、有机膦、亚砜的构型翻转理解元素有机化合物结构的影响因素

引用本文: 盛天祺, 杨雪楠, 李朝阳, 张韶光. 从有机胺、有机膦、亚砜的构型翻转理解元素有机化合物结构的影响因素[J]. 大学化学, 2026, 41(7): 415-429. doi: 10.12461/PKU.DXHX202505012 shu

Citation: Tianqi Sheng, Xuenan Yang, Zhaoyang Li, Shaoguang Zhang. Understanding structural influences in organoelement compounds through configurational inversion of amines, phosphines, and sulfoxides[J]. University Chemistry, 2026, 41(7): 415-429. doi: 10.12461/PKU.DXHX202505012 shu

从有机胺、有机膦、亚砜的构型翻转理解元素有机化合物结构的影响因素

盛天祺 ^1, ,
杨雪楠 ^1, ,
李朝阳 ^2, ,
张韶光 ^{2,
,}

1.
清华大学探微书院, 北京 100084;
2.
清华大学化学系, 生命有机磷化学及化学生物学教育部重点实验室, 北京 100084

通讯作者: 张韶光,Email:sgzhang@mail.tsinghua.edu.cn

基金项目:
清华大学本科教育教学改革项目

国家自然科学基金(22101151)

摘要: 氮(胺)、磷(膦)、硫(亚砜)中心手性化合物虽同为sp³杂化构型，但其构型翻转能垒和速率差异显著，导致手性异构体分离难度不同。本文以三者为例，系统探讨影响翻转能垒的核心因素，指出根本差异在于中心原子本身。这凸显“元素性质决定结构反应特性”的元素有机化学基本规律，旨在引导学生建立基于电子结构的理解路径。

关键词:

English

Understanding structural influences in organoelement compounds through configurational inversion of amines, phosphines, and sulfoxides

1.
Tanwei College, Tsinghua University, Beijing 100084, China;
2.
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China

Corresponding author: Shaoguang Zhang, sgzhang@mail.tsinghua.edu.cn

Received Date: 08 May 2025
Revised Date: 31 July 2025
Available Online: 17 October 2025

Abstract: Although nitrogen (amine), phosphorus (phosphine), and sulfur (sulfoxide) centered chiral compounds all adopt sp³-hybridized configurations, they demonstrate markedly different energy barriers and rates for configurational inversion, resulting in varying degrees of difficulty in chiral isomer separation. Using these three compound classes as representative examples, this study systematically examines the key factors governing inversion barriers. The analysis reveals that the fundamental distinction originates from the inherent properties of the central atoms, thereby illustrating the foundational principle of organoelement chemistry that “elemental characteristics determine structural and reactivity features”. This work aims to help students develop an electron structure-based approach for understanding structure-reactivity relationships.

Key words:

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从有机胺、有机膦、亚砜的构型翻转理解元素有机化合物结构的影响因素

通讯作者: 张韶光,Email:sgzhang@mail.tsinghua.edu.cn

English

Understanding structural influences in organoelement compounds through configurational inversion of amines, phosphines, and sulfoxides

Corresponding author: Shaoguang Zhang, sgzhang@mail.tsinghua.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

从有机胺、有机膦、亚砜的构型翻转理解元素有机化合物结构的影响因素

通讯作者: 张韶光,Email:sgzhang@mail.tsinghua.edu.cn

English

Understanding structural influences in organoelement compounds through configurational inversion of amines, phosphines, and sulfoxides

Corresponding author: Shaoguang Zhang, sgzhang@mail.tsinghua.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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