Detection of 1 H -Triphosphirene ( c -HP 3 ) and 2-Triphosphenylidene (HP 3 ): The Isovalent Counterparts of 1 H -Triazirine ( c -HN 3 ) and Hydrazoic Acid (HN 3 )
Detection of 1 H -Triphosphirene ( c -HP 3 ) and 2-Triphosphenylidene (HP 3 ): The Isovalent Counterparts of 1 H -Triazirine ( c -HN 3 ) and Hydrazoic Acid (HN 3 )
复制标题
1 H -三磷烯 ( c -HP 3 ) 和 2-三磷亚苯基 (HP 3 ) 的检测： 1 H -三嗪 ( c -HN 3 ) 和叠氮酸 (HN 3 ) 的等价对应物
DOI：
10.1021/acs.jpclett.2c00639
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Kaiser, Ralf I.
中科院分区：
文献类型：
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作者：
Zhang, Chaojiang;Zhu, Cheng;Eckhardt, André K.;Kaiser, Ralf I.
在低温基质中制备了迄今难以得到的1H-triphosphirene（c-HP 3）和2-triphosphenylidene（HP 3）分子，并通过光电离-反射飞行时间质谱（PI-ReTOF-MS）选择性地检测异构体。我们的研究结果揭示了一个化学上优选的环状异构体（c-HP 3）相比，非环状结构（HP 3），在对比有利于叠氮酸（HN 3）相比，1H-三氮杂环丙烷（c-HN 3）的等价HN 3系统。理论计算表明1H-三磷杂环戊二烯（c-HP 3）的环应变能仅为35 kJ mol-1，显著低于四面体磷分子（P4）的74 kJ mol-1。这项工作提供了一个基本的基准，以了解环状分子的电子结构和化学键合，并提供了一个非常规的方法来制备高度紧张，仍然难以捉摸的分子，如1H-三氮杂环丙烷和四面体四氮（N4）在不久的将来涉及渐进的非平衡化学。
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 HN3system 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.