Reactions of singlet phosphinidene and its hydroxy derivative with polar molecule hydrogen fluoride |
| |
| Authors: | Ping Yin Hegen Zheng Gui Yin Jiang Zhang Song Ye |
| |
| Institution: | 1. School of Chemistry and Materials Science , Yantai Normal University , Yantai 264025, P.R. China yinping426@163.com;3. Department of Chemistry, State Key Laboratory of Coordination Chemistry , Nanjing University , Nanjing 210093, P.R. China;4. School of Chemistry and Materials Science , Yantai Normal University , Yantai 264025, P.R. China |
| |
| Abstract: | The reaction mechanism of singlet phosphinidene and its hydroxy derivative with hydrogen fluoride has been investigated at the HF/6-311+G(d,p) and CCSD (T)/6-311+G(d,p) levels etc. in order to better understand their reactivity. The research results show both of them have two parallel reaction channels: channel (1) (or (3)) is an addition reaction with a three-membered ring transition state (TS) and channel (2) (or (4)) is a dehydrogenation (or dehydration) reaction with a four-membered ring TS. Furthermore, the thermodynamic and kinetic properties of these reaction channels were also examined, using the general statistical thermodynamics and Eyring transition state theory with Wigner correction. It is concluded that channel 1 is thermodynamically favoured over channel (2) especially at low temperature, and is kinetically favoured over channel (2) especially at high temperature. Moreover, it also favours these over reaction (3) while the singlet phosphinidene is substituted by the hydroxy group. |
| |
| Keywords: | |
|
|
