Experimental and theoretical examinations of n→σ* negative hyperconjugation in pyridinium dichlorophosphinomethylide |
| |
| Authors: | Raj K Bansal Neelima Gupta K Karaghiosoff P Mayer M Vogt |
| |
| Institution: | a Department of Chemistry, University of Rajasthan, Jaipur 302 004, India
b Department Chemie und Biochemie, Ludwig-Maximilians-Universität, Butenandtstr. 5-13, D-81377 München, Germany |
| |
| Abstract: | An X-ray crystal structure investigation as well as theoretical DFT (hybrid B3LYP/6-31G** level) calculations of 2-ethylpyridinium dichlorophosphino-ethoxycarbonylmethylide confirm the existence of significant n→σ* negative (anionic) hyperconjugation between the ylidic charge and the σ*P-Cl bond in the most stable conformer, which has the phosphorus lone pair oriented orthogonally to the ylidic pz orbital, resulting in elongation of the P-Cl bond parallel to the pz orbital but shortening of the C-P bond. |
| |
| Keywords: | Negative hyperconjugation Pyridinium dichlorophosphinomethylides X-ray structure B3LYP calculations Bis(pyridinium ylidyl)phosphenium chlorides |
| 本文献已被 ScienceDirect 等数据库收录！ |
