Detection of 1H-Triphosphirene (c-HP3) and 2-Triphosphenylidene (HP3): The Isovalent Counterparts of 1H-Triazirine (c-HN3) and Hydrazoic Acid (HN3),The Journal of Physical Chemistry Letters

当前位置： X-MOL 学术 › J. Phys. Chem. Lett. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Detection of 1H-Triphosphirene (c-HP3) and 2-Triphosphenylidene (HP3): The Isovalent Counterparts of 1H-Triazirine (c-HN3) and Hydrazoic Acid (HN3)
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2022-03-21 , DOI: 10.1021/acs.jpclett.2c00639
Chaojiang Zhang _{1,

2} , Cheng Zhu _{1,

2} , André K Eckhardt ₃ , Ralf I Kaiser _{1,

2}

Affiliation

The hitherto elusive 1H-triphosphirene (c-HP₃) and 2-triphosphenylidene (HP₃) molecules were prepared in low-temperature matrices and detected isomer selectively through photoionization coupled with reflectron time-of-flight mass spectrometry (PI-ReTOF-MS). Our results reveal a thermodynamically preferred cyclic isomer (c-HP₃) compared to the acyclic structure (HP₃) in contrast to the isovalent HN₃ system favoring hydrazoic acid (HN₃) compared to 1H-triazirine (c-HN₃). Theoretical computations suggest a ring strain energy of 1H-triphosphirene (c-HP₃) of only 35 kJ mol^–1, which is significantly lower than the tetrahedral phosphorus molecule (P₄) of 74 kJ mol^–1. This work provides a fundamental benchmark to understand the electronic structure and chemical bonding of cyclic molecules and offers an unconventional approach to preparing highly strained, still elusive molecules such as 1H-triazirine and tetrahedral tetranitrogen (N₄) in the near future involving progressive nonequilibrium chemistries.

中文翻译：

1H-三膦 (c-HP3) 和 2-三亚膦 (HP3) 的检测：1H-三氮杂环丙烷 (c-HN3) 和叠氮酸 (HN3) 的等价对应物

迄今为止难以捉摸的 1 H-三膦 ( c -HP ₃ ) 和 2- 三亚膦 (HP ₃ ) 分子是在低温基质中制备的，并通过光电离结合反射器飞行时间质谱 (PI-ReTOF-小姐）。我们的研究结果表明，与无环结构 (HP ₃ ) 相比，热力学上优选的环状异构体 ( c -HP ₃ ) 与等价 HN ₃系统相比，与 1 H-三氮杂环丙烷 ( c -HN ₃ ) 相比有利于叠氮酸 (HN ₃ ) . 理论计算表明环应变能为 1H-三膦 ( c -HP ₃ ) 仅为 35 kJ mol ^–1，明显低于74 kJ mol ^{–1的四面体磷分子 (P}₄ ) 。这项工作为了解环状分子的电子结构和化学键合提供了一个基本基准，并提供了一种非常规的方法来在不久的将来制备高应变、仍然难以捉摸的分子，如 1 H-三氮杂环和四面体四氮 (N ₄ )，包括渐进式非平衡化学。

更新日期：2022-03-21

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南