Pressure Tuning Spectroscopy of Metal Cluster Compounds and Organometallics
Roginski, Robert Theodore
This item is only available for download by members of the University of Illinois community. Students, faculty, and staff at the U of I may log in with your NetID and password to view the item. If you are trying to access an Illinois-restricted dissertation or thesis, you can request a copy through your library's Inter-Library Loan office or purchase a copy directly from ProQuest.
Permalink
https://hdl.handle.net/2142/69790
Description
Title
Pressure Tuning Spectroscopy of Metal Cluster Compounds and Organometallics
Author(s)
Roginski, Robert Theodore
Issue Date
1988
Doctoral Committee Chair(s)
Drickamer, Harry G.,
Department of Study
Chemical Engineering
Discipline
Chemical Engineering
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(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.
Use this login method if you
don't
have an
@illinois.edu
email address.
(Oops, I do have one)
IDEALS migrated to a new platform on June 23, 2022. If you created
your account prior to this date, you will have to reset your password
using the forgot-password link below.
