物理化学学报 >> 2003, Vol. 19 >> Issue (02): 125-129.doi: 10.3866/PKU.WHXB20030207

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磷炔R-C≡P(R=－BH2,－CH3,－NH2,－OH)及其异构体的稳定性

于海涛;池玉娟;傅宏刚;李泽生;孙家锺   

  1. 黑龙江大学化学化工学院，哈尔滨　150080；吉林大学理论化学研究所， 理论化学计算国家重点实验室，长春　130023
  • 收稿日期:2002-06-04 修回日期:2002-07-15 发布日期:2003-02-15
  • 通讯作者: 傅宏刚 E-mail:fuhg@hlju.edu.cn

The Stability of Phosphaalkynes R-C≡P (R=－BH2, －CH3,－NH2, －OH) and Their Isomers

Yu Hai-Tao;Chi Yu-Juan;Fu Hong-Gang;Li Ze-Sheng;Sun Jia-Zhong   

  1. College of Chemistry and Chemical Engineering, Heilongjiang University, Harbin　150080;State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun　130023
  • Received:2002-06-04 Revised:2002-07-15 Published:2003-02-15
  • Contact: Fu Hong-Gang E-mail:fuhg@hlju.edu.cn

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摘要： 采用B3LYP和CCSD(T)方法对R－C≡P(R=－BH2, －CH3,－NH2, －OH)体系进行了理论研究.结果表明，含C≡P三键的异构体BH2－C≡P和CH3－C≡P在各自的体系中分别是热力学最稳定的结构.而在HO－C≡P和NH2－C≡P体系中，热力学最稳定的结构却是H－P=C=O和含C≡N三键的N≡C－PH2.动力学理论研究表明，没有相关实验研究的R－C≡P(R=－BH2, NH2)体系中共有5种异构体是动力学稳定的. 在HO－C≡P体系的2种动力学稳定的异构体中， H－P=C=O连接方式的异构体已被实验所证实，而另外一种HO－C≡P连接方式的异构体的动力学稳定性较高，实验中可以观察到.对于CH3C≡P体系，研究所预示的2种动力学稳定的异构体中CH3－C≡P已被实验证实，从理论上推测另一种动力学稳定性较高的异构体HC≡C－PH2在实验中也可以检测到.

关键词: 磷炔, 异构化, 动力学稳定性

Abstract: B3LYP and CCSD(T) methods were employed to investigate the systems of R－C≡P(R=－BH2, －CH3,－NH2, －OH). The results indicate that isomers P≡C－BH2 and CH3－C≡P containing C≡P triple bond are thermodynamically the most stable species in BH2－C≡P and CH3－C≡P systems, respectively. But in the systems of HO－C≡P and NH2－C≡P, H－P=C=O and N≡C－PH2 containing C≡N triple bond are thermodynamically the most stable species, respectively. The calculated results on the kinetic stability indicate that for R－C≡P(R=－BH2,－NH2) systems, in which no experimental information are available, five isomers are kinetically stable. In HO－C≡P system, two kinetically stable species are located. Isomer H－P=C=O has been detected in experiment, and in view of higher kinetic stability, another isomer HO－C≡P should be experimentally observable. For CH3－C≡P system, isomer CH3－C≡P has been observed in experiment, and another kinetically stable isomer HC≡C－PH2 ought to be detected in future experiments.

Key words: Phosphaalkyne, Isomerization, Kinetic stability