Pressure Tuning Spectroscopy of Metal Cluster Compounds and Organometallics

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemical Engineering

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

1988

Author dc:creator

• Roginski, Robert Theodore

Contributors dc:contributor

• Drickamer, Harry G.,

• Chemistry, Inorganic
• Engineering, Chemical

Identifier

(UMI)AAI8815415

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/69790