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Theoretical Insights into the Bonding in Thorium Organometallic Complexes: A Comparison with Group IV Transition Metal Chemistry


Brusich, Mark John (1988) Theoretical Insights into the Bonding in Thorium Organometallic Complexes: A Comparison with Group IV Transition Metal Chemistry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/89jn-7f38.


In this thesis a detailed ab initio theoretical study of organothorium chemistry is presented. The first part is devoted to examining both the bonding in and the reaction chemistry of various substituted thorium complexes. Using the chlorine ligand as a model for the usual cyclopentadienyl groups found in these systems, we examine the bonding of hydrogen and methyl ligands to thorium. Frequent comparisons with the experimental results on similar species are made. In addition, by contrasting the bonding in the thorium complexes with the bonding in the analogous Group IVB systems, a qualitative and quantitative picture of bonding, as the atomic number of the metal becomes larger, can be obtained. The reaction chemistry is studied via two different sets of processes. In the first, the deuterium (D2) exchange reaction with a thorium-hydrogen bond is examined. Several studies have been done previously, both experimentally and theoretically, on the Group IVB exchange reactions. Hence, there is enough information to see trends and to make predictions about relative reaction rates. Also, from our investigation the effect that different types of ligands have on the activation barrier to reaction can be ascertained.

In the second part of the thesis, the factors that go into stabilizing bond formation are discussed concerning both main group elements and transition metals, including actinides. In particular, the process of bond formation between hydrogen atom and the alkali metals is compared with the same process in the Group IVB-hydrogen and thorium-hydrogen saturated complexes. The main difference between the alkali metal and the transition metal bonds with hydrogen is the bond strength trends with increasing atomic number. For the alkali metals the bond energies decrease down the column, yet for the transition metals and thorium it is the reverse. The conclusion is that the shape of the mostly d in character transition metal bonding orbitals is such that better overlap can be achieved with hydrogen as the orbitals become more diffuse. In the alkali metals the bonds can be described as s—s bonds whose overlap decreases with increasing diffuseness.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Goddard, William A., III
Thesis Committee:
  • Gray, Harry B. (chair)
  • Goddard, William A., III
  • Grubbs, Robert H.
  • Weinberg, William Henry
Defense Date:14 March 1988
Funding AgencyGrant Number
Record Number:CaltechTHESIS:10192009-085412529
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Appendix A.
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:5307
Deposited By: Tony Diaz
Deposited On:04 Nov 2009 21:54
Last Modified:19 Apr 2021 22:37

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