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 Title: Pressure Tuning Spectroscopy of Metal Cluster Compounds and Organometallics Author(s): Roginski, Robert Theodore Doctoral Committee Chair(s): Drickamer, Harry G., Department / Program: Chemical Engineering Discipline: Chemical Engineering Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Chemistry, Inorganic Engineering, Chemical Abstract: The effect of hydrostatic pressure upon various metal cluster compounds and organometallics was studied through the use of electronic absorption and infrared spectroscopies. The systems studied were chosen for their use as potential models for chemisorbed metallic surfaces, and to gain a better fundamental understanding of metal-carbon interactions. In particular, it was found that: (1) the highly symmetric metal cluster compund Re$\sb3$Cl$\sb \sp{3-}$ affords the opportunity to measure the relative energy shifts of two occupied bonding electronic levels (as well as two unoccupied antibonding levels; (2) pressure can serve to cause a torsional isomerization in binuclear metal cluster compounds, even when the two metal atoms are bonded to bridging ligands; (3) the interpretation of pressure shifts, in conjunction with electronic structural calculations, can produce a reasonable set of assignments for the visible absorption spectrum of the platinum cluster compound (Pt$\sb3$(CO)$\sb6\rbrack\sb2\sp{2-}$; (4) pressure can induce an order-disorder phase transition in the solid state for (Fe(cp)$\sb2$) PF$\sb6$; (5) the splittings between d-orbitals and electronic repulsion parameters can determine as a function of pressure for metallocenes; (6) pressure can greatly enhance intermolecular interactions between metallocenes in the solid state, thereby drastically affecting the infrared spectra for these molecules. Issue Date: 1988 Type: Text Description: 170 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988. URI: http://hdl.handle.net/2142/69790 Other Identifier(s): (UMI)AAI8815415 Date Available in IDEALS: 2014-12-15 Date Deposited: 1988
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