Rhodium-mediated stereoselective polymerization of 'carbenes'
| Autor: | Vincenzo Busico, Valeria Van Axel Castelli, W.I. Dzik, Coen Hendriksen, Michele Vacatello, Erica Jellema, Jan M. M. Smits, Tom G. Bloemberg, Ernst R. H. van Eck, Bas de Bruin, Dennis G. H. Hetterscheid, A. L. Segre, Alan E. Rowan |
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| Přispěvatelé: | Homogeneous and Supramolecular Catalysis (HIMS, FNWI), Hetterscheid, D. G. H., Hendriksen, C, Dzik, W, Smits, J. M. M., VAN ECK, E. R. H., Rowan, A. E., Busico, Vincenzo, Vacatello, Michele, VAN AXEL CASTELLI, V, Segre, A, Jellema, E, Bloemberg, T. G., DE BRUIN, B. |
| Rok vydání: | 2006 |
| Předmět: |
Reaction mechanism
High molecular mass Molecular Materials Radical polymerization chemistry.chemical_element General Chemistry Solid State NMR Biochemistry Medicinal chemistry Catalysis Analytical Chemistry Rhodium chemistry.chemical_compound End-group Colloid and Surface Chemistry chemistry Polymerization Ethyl diazoacetate Organic chemistry Stereoselectivity |
| Zdroj: | Journal of the American Chemical Society, 128(30), 9746-9752. American Chemical Society Journal of the American Chemical Society, 128, 9746-9752 Journal of the American Chemical Society, 128, 30, pp. 9746-9752 |
| ISSN: | 0002-7863 |
| Popis: | Contains fulltext : 35468.pdf (Publisher’s version ) (Open Access) Unprecedented rhodium-catalyzed stereoselective polymerization of "carbenes" from ethyl diazoacetate (EDA) to give high molecular mass poly(ethyl 2-ylidene-acetate) is described. The mononuclear, neutral [(N, O-ligand) M-I(cod)] (M) Rh, Ir) catalytic precursors for this reaction are characterized by (among others) single-crystal X-ray diffraction. These species mediate formation of a new type of polymers from EDA: carbon-chain polymers functionalized with a polar substituent at each carbon of the polymer backbone. The polymers are obtained as white powders with surprisingly sharp NMR resonances. Solution and solid state NMR data for these new polymers reveal a highly stereoregular polymer, with a high degree of crystallinity. The polymer is likely syndiotactic. Material properties are very different from those of atactic poly(diethyl fumarate) polymer obtained by radical polymerization of diethyl fumarate. Other diazoacetates are also polymerized. Further studies are underway to reveal possible applications of these new materials. |
| Databáze: | OpenAIRE |
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