

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 Brian E. Hanson Committee Chair Karen J. Brewer none Paul A. Deck none Keywords
- water-soluble phosphines
- two-phase
- hydroformylation
- olefins
- asymmetric hydrogenation
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-(3-phenylpropyl)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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