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Future WorksVerification 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.
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.
Phosphine Ligand Synthesis: A Tale of Heavy MetalsAnthony R. Spyker*, Troy Luster*, Shannon M. Biros and John E. Bender
Department of Chemistry, Grand Valley State University, Allendale, MI 49401
Introduction
Complex 1H Nuclear Magnetic Resonance
With the shortage of fossil fuels, massive oil spills, and an increase inpopulation, the demand for a more sustainable energy source has increased.In order to adjust to the high demand, many countries have begun usingnuclear energy because of its ability to produce a significant amount ofenergy with low carbon emissions. However, nuclear energy produceswaste that (if not contained) can cause environmental and health issues dueto the presence of radioactive elements. In order to reduce the negativeimpact nuclear waste can have on the environment, efforts are taken toseparate actinides and lanthanides from one another. These two wasteproducts are generally produced in mixture after what fuel has been used.For this project, a majority of the focus was placed on heavy metal, andlanthanide extractions. Lanthanides can be used to to produce gasolinefrom crude oil, and help with the colorization of TV screens and lenses. Byusing multiple derivatives made from diphenyl-2-thienyl phosphine, andBis(2-methoxyphenyl)phenyl phosphine, we hope to find a way toselectively bind to f-elements in order to extract these heavy metals,rendering the nuclear waste useful again.
Reactions and Synthesis:
ResultsThrough 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(2-methoxyphenyl)phenyl phosphine was shown to complex with platinum, shown through 31PNMR (31P{1H}(161.28MHz)CDCl3δ(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(2-thienyl)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, 1J195Pt-31P =3678.14Hz, P=Pt), and finally the 4:1 ratio reported:
31P{1H} (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
1HNMR at 400MHz
Cis or Trans Bis[(diphenyl)-2-thiophenylphosphino] platinum (II) dichloride
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., InorganicaChimica Acta. 1985, 187
31PNMR Phosphine and Oxide
31PNMR Free Phosphine
31PNMR Oxide & Ag
31PNMR Phosphine & Pt
31PNMR Free Phosphine