Affiliation:
1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China
Abstract
Theoretical investigations are preformed on the model reaction of PH 3 CH + H 2 CO to unravel reactivity of PH 3 CH , so-called Ylide-like radical, at G3MP2 and CCSD(T)/aug-cc-pVDZ//MP2/6-311++G(d,p) level. The results indicate that P -Ylidic radical behaves differently from the P -Ylide or usual unsaturated radical toward formaldehyde. For the entrance channels, [2+2] cycloaddition to form oxaphosphetane radical INT1 is more favorable, which is an analogical process to Witting reaction of P -Ylide. So PH 3 CH shows P -Ylide character in entrance channel, which has found the support from the dual one-center frontier–orbital interaction based on Fukui's frontier–orbital theory. However, due to the radical character of INT1, it can competitively give P2 PH 3 CHCHO + H and INT2, but not Witting-type products of alkene and phosphine oxide. At last, INT2 almost can barrierlessly fragmentate to Corey-type products of ethene oxide radical and phosphine. The present study shows that PH 3 CH , Ylide-like radical, has duplicate reactivity of both P-Ylide and radical, and title reaction presents a completely new reaction mechanism, compared with previous well-known H -abstract or addition–elimination mechanism for radical- H 2 CO reactions.
Publisher
World Scientific Pub Co Pte Lt
Subject
Computational Theory and Mathematics,Physical and Theoretical Chemistry,Computer Science Applications
Cited by
1 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献