Aromaticity and activation strain analysis of [3 + 2] cycloaddition reactions between group 14 heteroallenes and triple bonds |
| |
Authors: | Fernández Israel Cossío Fernando P Bickelhaupt F Matthias |
| |
Institution: | Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040 Madrid, Spain. israel@quim.ucm.es |
| |
Abstract: | We have computationally explored the trend in reactivity of 3 + 2] cycloaddition reactions between H(2)E=C=PH and HC≡CH as the terminal position in the phosphaallene is varied along E = C, Si, Ge, Sn, Pb. The reaction barrier drops significantly from E = C (nearly 50 kcal/mol) to E = Si-Pb (ca. 20 kcal/mol). Activation strain analyses tie this trend to a reduction in activation strain in the heavier phosphaallene analogues which, in contrast to the parent compound H(2)C=C=PH, do already possess the bent geometry required in the TS. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|