Identifier
etd-04222012-152528
Degree
Doctor of Philosophy (PhD)
Department
Chemistry
Document Type
Dissertation
Abstract
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 believe this was caused by water-gas shift chemistry (H2O + CO = H2 + CO2). However, a subsequent experiment in a Parr autoclave showed that the process was not fast or efficient enough to serve as a hydrogen source for hydroformylation. The cationic character of the dirhodium catalyst was utilized for its attachment to the surface of silica gel. The purpose of immobilization is to enable easy separation of the catalyst from hydroformylation products. At room temperature in dichloromethane solution the immobilization was successful, but during hydroformylation conditions in acetone, the catalyst was released into solution.
Date
2012
Document Availability at the Time of Submission
Release the entire work immediately for access worldwide.
Recommended Citation
Polakova, Darina, "Studies on a dirhodium tetraphosphine hydroformylation catalyst" (2012). LSU Doctoral Dissertations. 1517.
https://repository.lsu.edu/gradschool_dissertations/1517
Committee Chair
Stanley, George G.
DOI
10.31390/gradschool_dissertations.1517