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Inorganic Periodic Table

Inorganic Periodic Table. Organic Periodic Table. C. H. N. O. F. B. metals. Li. Si. P. S. Cl. Na. Mg. Br. K. I. metals. Phosphine Ligands. Commonly utilized inorganic ligand Key Properties (all readily controlled) sterics sigma donation (electronics)

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Inorganic Periodic Table

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  1. Inorganic Periodic Table

  2. Organic Periodic Table C H N O F B metals Li Si P S Cl Na Mg Br K I metals

  3. Phosphine Ligands • Commonly utilized inorganic ligand • Key Properties (all readily controlled) • sterics • sigma donation (electronics) • pi-acidity (orbital ?’s)

  4. Phosphine Manipulation • Sterics—Simple as changing the hydrocarbon ligand (Me, Et, tBu, Ph, etc) • s-donor / p-acceptor character not as simple

  5. Survey of Typical OM Ligands P(tBu)3 P(CxF2x+1)3 PPh3 olefins P(OPh)3 PF3 Size PMe3 P(OMe)3 CO Electron Acceptor Ability - few ligands bridge the electronic gap - massive voids were recently noted [Cundari, JACS, 2003, 4318]

  6. Our Approach—bridge the gap • Prepare phosphine ligands with an electronic influence of P(OR)3 • Modification of PR3 framework with Rf • Similar to F/H swap • Chose Rf = C2F5, sought R2PRf series • R = Me, Et, iPr, tBu, Ph

  7. Ligand Preparation Note stability difference of lithium reagent HFC procedure developed Affectionately called pfepp (pentaflouroethyl)diphenylphosphine

  8. pfepp—a Good Start… • Modify typical (PR3) framework • Common thread—replace R with Rf (Rf = C2F3 or C2F5) • Substitute other R‘s with (C, N, O) based substituents

  9. Other Ligands After pfepp • Have prepared many others of the form R2—P—C2F5 R = NEt2 , N(pyrrole), N(pyrrolidine) ALL have student chosen nicknames (you make it, you name it).

  10. pfepp Coordination Chemistry Straightforward reaction, alkane solvent Establish electronic influence of ligand Also prepared other molly compounds

  11. pepy molly—sounds like a cheerleader…doesn’t it?

  12. Ru3(CO)12 Starting material • smooth substitution {Ru(CO)3(pepy)}3 • Clusters of this type insert into C—S bonds • fluorovinyl derivative

  13. Hydrogenation Chemistry • Examined reduction of simple alkenes • Conditions pretty extreme • Also worked for cyclohexene and 1-decene

  14. Acknowledgements --University of Memphis --National Science Foundation -- Jennifer Phelps -- Dr. Jason Palcic -- Sara Frawley -- Dr. Russ Baughman -- Jennifer Seat -- Dr. Dean Roddick -- Misha Golynskiy -- Karl Pittard -- Mary Ross -- Johnny Giles

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