부산대학교 도서관

To link to full-text access for this article, visit this link: http://dx.doi.org/10.1016/j.theochem.2005.08.015 Byline: Ping Yin (a), Hegen Zheng (b), Gui Yin (b), Taoyu Zhou (c), Yanzhi Sun (a) Abstract: The insertion reaction mechanism of singlet phosphinidenes XP (X=H, Li, F, Cl, OH, SH) with polar hydrogen chloride molecule has been investigated at B3LYP/6-311+G(d, p) level in order to better understand their reactivity. Furthermore, the general statistical thermodynamics and Eyring transition state theory with Wigner correction were used to examine the temperature influences on the thermodynamic and kinetic properties of these reaction channels during the temperature range of 200-1000K. It is concluded that with the rise of the temperature, the reaction equilibrium constant K decreases sharply, while the reaction rate constant k increases slowly for all these insertion reactions, and the reaction channel of LiP with HCl has both thermodynamic and kinetic advantages comparing with other concerned reactions, especially at high temperature. Author Affiliation: (a) Department of Chemistry, School of Chemistry and Materials Science, Yantai Normal University, No. 184, Road Hongqi, Yantai, Shandong 264025, People's Republic of China (b) State Key Laboratory of Coordinate Chemistry, Department of Chemistry, Nanjing University, Nanjing 210093, People's Republic of China (c) School of Materials Science and Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China Article History: Received 6 July 2005; Revised 26 July 2005; Accepted 4 August 2005