Open Access. Powered by Scholars. Published by Universities.®
Physical Sciences and Mathematics Commons™
Open Access. Powered by Scholars. Published by Universities.®
Articles 1 - 2 of 2
Full-Text Articles in Physical Sciences and Mathematics
Studies Of A Dirhodium Tetraphosphine Catalyst For Hydroformylation And Aldehyde-Water Shift Catalysis, Aaron Rider Barnum
Studies Of A Dirhodium Tetraphosphine Catalyst For Hydroformylation And Aldehyde-Water Shift Catalysis, Aaron Rider Barnum
LSU Doctoral Dissertations
Research into the dirhodium tetraphosphine catalyst precursor [rac-Rh2(nbd)2(et,ph-P4)](BF4)2 shows it is capable of forming a highly active and regioselective hydroformylation catalyst in situ when using an acetone or acetone/water solvent. Hydroformylation experiments (using 1-hexene), FT-IR studies, and acid-base studies were performed to better understand the various complexes of the dirhodium catalyst cycle. These studies lead to the newly proposed catalyst mechanism when performed in an acetone/water solution, using the monocationic [rac-Rh2(H)(µ-CO)2(CO) (et,ph-P4)]+ as the proposed active catalyst complex for hydroformylation. For the conversion of 1-hexene to heptanal, it is capable of performing an initial rate of 30 turnovers per min, …
Studies On A Dirhodium Tetraphosphine Hydroformylation Catalyst, Darina Polakova
Studies On A Dirhodium Tetraphosphine Hydroformylation Catalyst, Darina Polakova
LSU Doctoral Dissertations
The dirhodium tetraphosphine catalyst [Rh2(nbd)2(rac-et,ph-P4)](BF4)2 was investigated in acetone and water/acetone in order to explain better hydroformylation results in the latter solvent. In-situ NMR spectroscopy showed slower degradation in water/acetone. Less tendency to form penta/hexacarbonyl complexes in water/acetone was shown by 31P{1H} NMR and FT-IR. A pH decrease and hydroformylation studies in presence of a base indicated formation of a monocationic monohydride species. A new reaction mechanism was suggested that takes into account the observed differences from the acetone solvent system. The presence of water enabled production of hydride species when the dirhodium catalyst was exposed to CO gas. We …