Complexos fosfínicos de rutênio : hidrogenação, ROMP - hidrogenação

• Autor(a) principal: Bogado, André Luiz
• Data de Publicação: 2007
• Tipo de documento: Tese
• Idioma: por
• Título da fonte: Repositório Institucional da UFSCAR
• Texto Completo: https://repositorio.ufscar.br/handle/ufscar/6134
• topic: Complexo inorgânico - rutênio; Catálise homogênea; Bifosfina; Carbeno; Fosfinocarbeno; Tandemcatálise; CIENCIAS EXATAS E DA TERRA::QUIMICA

ON THE RUTHENIUM PHOSPHINIC COMPLEXES: HYDROGENATION, ROMP-HYDROGENATION is a concise explanation about the ruthenium chemistry with donor bulky electron-rich biphosphines as precursor unity to prepare ruthenium carbon moiety. The complexes synthesized were applied as precatalyst on the hydrogenation of double bonds and non polar double bonds, as well as precatalyst on the assisted tandem catalyses of cyclooctene, ROMP Hydrogenation. The dihydride complex [RuH(dtbpm)]2-μ- (Cl)2 have been applied with good results as a precatalyst at mild conditions to hydrogenate polar and non polar double bonds, and remarkable activity over a substrate containing both kind of bonds. The regioseletivity can be managed by simple modification on the variable conditions of the system, applying different solvent, auxiliary ligands trigged on the course of the reaction, and addition of co-catalyst. By the way, the complex [RuH(dtbpm)]2-μ-(Cl)2 is a powerful precursor to afford new hydride complexes containing ruthenium. In the fact of this view, the complex [RuHCl(dtbpm)(bipy)] achieved from [RuH(dtbpm)]2-μ-(Cl)2 is the first mono hydride complex, that is active on the reduction of acetophenone without base conditions. The photochemistry behaviour of the vinylidene complexes containing ruthenium II obtained from the isomerization and -η2 coordination of the phenylacetylene was studied, with special attention to the complex [RuCl2(PPh3)2(bipy)(=C=CHPh)](PF6), which presents an intense emission centrated at 460 nm, when excitated between 300 400 nm at room temperature. The first coordination of the ligand 1-tert-butil-3-(di-tertbutilphosphinomethyl) imidazol-2-ilidene (CNCP) on the ruthenium centre is describing to afford the complex [RuCl(CNCP-κ2(C2,P))]2-μ-(Cl)2.The last one is a well defined binuclear ruthenium (II) complex with 16 electron valence in two chloride bridge, stabilized by the bulky, electron-rich chelating ligand (CNCP).