Phosphine Ligand Synthesis: A Tale of Heavy Metals
Anthony R. Spyker*, Troy Luster*, Shannon M. Biros and John E. Bender
Department of Chemistry, Grand Valley State University, Allendale, MI 49401
Introduction
Reactions and Synthesis:
With the shortage of fossil fuels, massive oil spills, and an increase in
population, the demand for a more sustainable energy source has increased.
In order to adjust to the high demand, many countries have begun using
nuclear energy because of its ability to produce a significant amount of
energy with low carbon emissions. However, nuclear energy produces
waste that (if not contained) can cause environmental and health issues due
to the presence of radioactive elements. In order to reduce the negative
impact nuclear waste can have on the environment, efforts are taken to
separate actinides and lanthanides from one another. These two waste
products are generally produced in mixture after what fuel has been used.
For this project, a majority of the focus was placed on heavy metal, and
lanthanide extractions. Lanthanides can be used to to produce gasoline
from crude oil, and help with the colorization of TV screens and lenses. By
using multiple derivatives made from diphenyl-2-thienyl phosphine, and
Bis(2-methoxyphenyl)phenyl phosphine, we hope to find a way to
selectively bind to f-elements in order to extract these heavy metals,
rendering the nuclear waste useful again.
31PNMR
Oxide & Ag
31PNMR
Phosphine and Oxide
31PNMR
Free Phosphine
31PNMR
Phosphine & Pt
31PNMR
Free Phosphine
Results
1HorNuclear
Complex Cis
Magnetic Resonance
Trans Bis[(diphenyl)-2-thiophenylphosphino]
platinum (II) dichloride
1HNMR
at 400MHz
Acknowledgements:
As part of the Grand Valley State University Chemistry Research Program, we would
like to thank Dr. Richard Staples of Michigan State University, all of the staff of the
GVSU Chemistry Department especially Profs. Richard Lord, Christopher Lawrence,
Jim Krikke, and William Winchester. We would like to thank the Office of Undergraduate
Research and Scholarship , the NSF, and The GVSU Weldon Fund for providing
financial support. And also Suzan Mendoza for her assistance in making our trip
possible.
Bibliography
1.) Ramsden C.A. Science of Synthesis, 2007, 31b, 2035 2.) Tanke R.S., Holt E. M., Crabree R. H. Inorg. Chem., 1991, 30(8), 1714 3.)
Muller A. Acta Cryst, 2011, E67, 089 4.) (a)Isslieb, K.; Krech, F.Z. Anorg. Allg. Chem. 1964, 328, 21. (b) Lahuerta, P.; Peris, E.; Sanau,
M.; Ubeda, M. A.; Garcia-Granda, S. J. Organomet. Chem. 1993, 445, C10. 5.)Aguado, R.; Arnaiz, F. J. Journal of Chemical Education.
1995, A196. 6.)D.W. Allen, J.R. Charlton, B.G. Hutley Phosphorus, 6(1976), 786 7.) Hope E. G., Levason W., Powell N. A., Inorganica
Chimica Acta. 1985, 187
Through trials it has been found that the phosphorous center of the
two ligands used, Bis(2-methoxyphenyl)phenyl phosphine and
diphenyl(2-thienyl)phosphine, complex well with the three
chalcogen column atoms in question (i.e. O, S, Se). The bis(2methoxyphenyl)phenyl phosphine was shown to complex with
platinum, shown through 31PNMR (31P{1H}(161.28MHz)CDCl3
δ(PPM):+7.717(s,w/d satalite, 1J195Pt-31P =2493.83Hz,P=Pt) giving some
indication of the trans orientation, further data including crystal
structure and some modeling needs to be done to confirm
orientation. The diphenyl(2-thienyl)phosphine oxide complex with
Lanthanum, showing a 31PNMR chemical shift from
δ(PPM):+20.267(CD3CN) to δ(PPM):+28.733(CD3CN). The diphenyl(2thienyl)phosphine reacted with Pt, which was also shown through
31PNMR. And depending on concentration, there would be one or
more peaks. When concentration was raised to a 2:1 ratio of ligand
to La spectral results reported; 31P {1H} ((161.84MHz) CDCl3,
δ(PPM):+10.8(s, w/ d satellites, 1J195Pt-31P =2648.35Hz, P=Pt), Raised to
a 3:1 ratio: 31P{1H} (161.83MHz) CDCl3, δ(PPM):+5.4(s, w/ d satellites,
1J
31P{1H}
=3678.14Hz,
P=Pt),
and
finally
the
4:1
ratio
reported:
195Pt-31P
(161.83MHz) CDCl3, δ(PPM):+5.4(s, w/ d satellites, 1J195Pt-31P
=3683.25Hz, P=Pt). Ligand formation with sulfur was found to
complex with silver, but further analysis needs to be performed to
assess orientation of interaction. Selenium did not have any
verifiable shifts observed on the 31PNMR when added with
lanthanum or silver
Future Works
Verification via crystal structures will have to be found for all of the ligands in complex with the heavy metals. This
includes platinum and silver as well as lanthanum and samarium. Further work will be done to confirm the effects
of the Bis(2-Methoxyphenyl)phenyl phosphine derivatives with the lanthanides and silver and platinum as well as
NMR interpretations for diphenyl(2-thionyl)phosphine and all of its derivative forms.