The synthesis and characterization of cyclopentadienylsilver and cyclopentadienylcopper complexes

• Main Author: Lettko, Linda
• Language: ENG
• Published: ScholarWorks@UMass Amherst 1995
• Subjects: Chemistry
• Online Access: https://scholarworks.umass.edu/dissertations/AAI9524726

The synthesis and characterization of cyclopentadienylsilver and cyclopentadienylcopper complexes have been studied. By reacting stoichiometric amounts of substituted cyclopentadienyl sodium salts with silver(I) trifluoromethanesulfonate in the presence of phosphines or directly with phosphine-silver(I) trifluoromethanesulfonate precursors, a series of new organosilver compounds have been prepared. Related organocopper compounds were obtained using bromotriphenylphos-phinecopper(I). These compounds have been studied by spectroscopic techniques including IR spectroscopy and multinuclear NMR spectroscopy. The reaction of triphenylphosphine, 1,2-bis(diphenylphosphino)-ethane, bis(diphenylphosphino)methane, or 1,1-bis(diphenylphosphino)-ethane with silver(I) trifluoromethanesulfonate in a 1:1 ratio led to complexes 44, 46, 47, and 49. Compound 45 was also produced by reacting triphenylphosphine with silver(I) trifluoromethanesulfonate in a 2:1 ratio. The new compounds were characterized by $\sp{31}{\rm P}$ NMR solution and solid state spectroscopy. These compounds could be reacted with various cyclopentadienyl derivatives to produce the corresponding cyclopentadienylsilver analogs. The organometallic silver compounds, 52, 54, 58, 59, 63-68 were prepared by reacting stoichiometric ratios of phosphine-silver(I) trifluoro-methanesulfonate precursors and the cyclopentadienyl derivatives, 51 or 53, in THF. The reaction conditions varied from -78$\sp\circ{\rm C}$ to room temperature. These compounds were found to be more air- and moisture-stable than the unsubstituted parent compound, 9. Compound 66 was characterized by X-ray crystallography techniques. Compound 66 exhibited an unusual bonding interaction between the silver atom and the cyclopentadienyl ring which is between $\eta\sp1$ and $\eta\sp3$ bonding. Several substituted cyclopentadienyl derivatives of copper using the triphenyl-phosphine ligand were also studied. Compounds 56 and 57 were characterized by IR spectroscopy and multinuclear NMR techniques which include solution and solid state spectra. Complexes utilizing the diphenylphosphinocyclopentadienyi ligand and the tetra- and pentaphenylcyclopentadienyl ligands have also been prepared. By using appropriate ratios of the substituted cyclopentadienide salts and a starting complex of the type (PR$\sb3){\rm MX},$ where R = Ph or Et, M = Ag or Cu and X = Cl or Br, silver and copper compounds 70-72, 75, 77, and 79 have been synthesized and characterized in this manner.