Title page for ETD etd-5217143049751491


Type of Document Master's Thesis
Author Kang, Jianxing
URN etd-5217143049751491
Title Water Soluble Phosphines, Their Transitional Metal Complexes, and Catalysts
Degree Master of Science
Department Chemistry
Advisory Committee
Advisor Name Title
Brewer, Karen J.
Deck, Paul A.
Hanson, Brian E. Committee Chair
Keywords
  • asymmetric hydrogenation
  • olefins
  • hydroformylation
  • two-phase
  • water-soluble phosphines
Date of Defense 1997-05-19
Availability unrestricted
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.

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