| Autor: |
Oishi Y; Division of Molecular Engineering, Kyoto University, Kyoto 606-01, Japan., Sakamoto E, Fujimoto H |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 1996 Jan 03; Vol. 35 (1), pp. 231-238. |
| DOI: |
10.1021/ic9504607 |
| Abstrakt: |
Mechanisms of palladium-catalyzed cycloaddition reactions of methylenecyclopropane with olefins and those of oxatrimethylenemethane (OTMM) and azatrimethylenemethane (ATMM) complexes with olefins have been studied by applying the ab initio molecular orbital method. Assuming an intramolecular coupling mechanism, we have examined some model complexes, Pd(eta(2)-methylenecyclopropane)(ethylene)(PH(3)) and Pd(eta(3)-OTMM or eta(3)-ATMM)(ethylene)(PH(3)), to determine the transition state structures. The coupling of methylenecyclopropane, OTMM, and ATMM with ethylene on the metal center takes place in two steps. In the reaction of methylenecyclopropane, the first step involves an opening of the cyclopropane ring promoted by an attack of ethylene. The methylenecyclopropane moiety has a pi-allylic form at the first transition state which leads to a metallacyclic intermediate. The first transition state of the reactions of OTMM and ATMM complexes looks very similar to that of the methylenecyclopropane complex, having pi-allylic coordinations. The two paths are separated in the second step. A [3 + 2] addition product is obtained by a reductive elimination from the intermediate metallacycle, whereas a prototropic shift followed by a reductive elimination affords a [2 + 1] addition product. It is the energetics of the second stage starting from the metallacycles that differentiates the reactions of the OTMM and ATMM complexes from the reaction of the methylenecyclopropane complex. The relative stabilities of various isomeric forms of these complexes have also been studied. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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