Water Soluble Phosphines, Their Transitional Metal Complexes, and Catalysts
| dc.contributor.author | Kang, Jianxing | en |
| dc.contributor.committeechair | Hanson, Brian E. | en |
| dc.contributor.committeemember | Deck, Paul A. | en |
| dc.contributor.committeemember | Brewer, Karen J. | en |
| dc.contributor.department | Chemistry | en |
| dc.date.accessioned | 2014-03-14T20:51:47Z | en |
| dc.date.adate | 1997-05-19 | en |
| dc.date.available | 2014-03-14T20:51:47Z | en |
| dc.date.issued | 1997-05-19 | en |
| dc.date.rdate | 1997-05-19 | en |
| dc.date.sdate | 1998-07-17 | en |
| dc.description.abstract | In recent years two-phase catalysis has been established as a new field of catalyzed processes and has achieved industrial-scale importance in olefin hydroformylation. Two-phase reactions have a number of advantages, for example, ease of separation of catalyst and product, catalysts can be tailored to the particular problem, use of special properties and effects of water as a solvent, and low environmental impact. For higher olefins (* C6), the reaction suffers low activity due to low water solubility of higher olefins. Tricesium analog of TPPTS, m,m,m-trisulfonated triphenylphosphine, was synthesized and fully characterized. Two-phase olefin hydroformylation with Rh(acac)(CO)2 was investigated. The results indicated that both activity and selectivity (linear to branch aldehyde ratio) are similar to Rh/TPPTS system. The salt effect showed that increase the solution ionic strength will increase the selectivity and decrease the activity in the olefin hydroformylation with TPPTS. A new surface active phosphine, trisulfonated tris-m-(3henylpropyl)phenylphosphine, was synthesized and fully characterized. The results of biphasic olefin hydroformylation were consistent with aggregation of the ligand. The two phase 1-octene hydroformylation results showed that with only 3 methylene groups, there is no difference between the para and meta position of C3 group. A new chelating diphosphine, tetrasulfonated 2,2'-bis{di[p-(3 phenylpropyl)phenyl]phosphinomethyl}-1,1'-biphenyl,was prepared and fully characterized. Its application in two-phase hydroformylation of olefin showed enhanced activity and selectivity compared to the non-chelated phosphine analog. Finally, homogeneous asymmetric hydrogenation was carried out in the presence of a chiral surfactant in an attempt to affect asymmetric induction. The catalytic results showed that at a surfactant/Rh ratio of 25, the asymmetric hydrogenation of AACA-Me (a-Acetamidocinnamic Acid Methyl Ester) in methanol has no effect on asymmetric induction with the introduction of this chiral surfactant. | en |
| dc.description.degree | Master of Science | en |
| dc.identifier.other | etd-5217143049751491 | en |
| dc.identifier.sourceurl | http://scholar.lib.vt.edu/theses/available/etd-5217143049751491/ | en |
| dc.identifier.uri | http://hdl.handle.net/10919/36782 | en |
| dc.publisher | Virginia Tech | en |
| dc.relation.haspart | etd.pdf | en |
| dc.rights | In Copyright | en |
| dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | en |
| dc.subject | asymmetric hydrogenation | en |
| dc.subject | olefins | en |
| dc.subject | hydroformylation | en |
| dc.subject | two-phase | en |
| dc.subject | water-soluble phosphines | en |
| dc.title | Water Soluble Phosphines, Their Transitional Metal Complexes, and Catalysts | en |
| dc.type | Thesis | en |
| thesis.degree.discipline | Chemistry | en |
| thesis.degree.grantor | Virginia Polytechnic Institute and State University | en |
| thesis.degree.level | masters | en |
| thesis.degree.name | Master of Science | en |
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