Computational study of c-h bond cleavage and c-c bond formation processes catalyzed by transition metal complexes
The first part of the thesis is mainly devoted to the mechanism of a C-H activation reaction by a niobium complex. The mechanism of C-H bond activation of benzene by the TpMe2NbCH3-(c-C3H5)-(MeCCMe) complex was rationalized. The key intermediate is an unusual 2-cyclopropene complex. We rationalized...
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| Tipo de recurso: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2012 |
| País: | España |
| Institución: | Universitat Rovira i virgili (URV) |
| Repositorio: | Repositori Institucional de la Universitat Rovira i Virgili |
| OAI Identifier: | oai:urv.cat:TDX:1043 |
| Acceso en línea: | https://hdl.handle.net/20.500.11797/TDX1043 http://hdl.handle.net/10803/79120 |
| Access Level: | acceso abierto |
| Palabra clave: | 544 - Química física |
| Sumario: | The first part of the thesis is mainly devoted to the mechanism of a C-H activation reaction by a niobium complex. The mechanism of C-H bond activation of benzene by the TpMe2NbCH3-(c-C3H5)-(MeCCMe) complex was rationalized. The key intermediate is an unusual 2-cyclopropene complex. We rationalized the selectivities obtained for the activation of several alkylaromatics by the 2-cyclopropene niobium complex. The intriguing role of the alkyne ligand of the same complex, and its possible role in the migration processes, was investigated. In the second part of the thesis, we focused on the silicon based cross-coupling. The results suggest than the transmetalation is easier after phosphine dissociation, and in presence of the bromide ligand on the palladium. The beneficial effect of dibenzylideneacetone on the coupling was clarified. |
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