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More Fun Than Anything


Harris, Daniel Charles (1973) More Fun Than Anything. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/XBQW-9V06.


An exhaustive study of piddling cyclopropenium salts is described. This includes synthesis, characterization and the study of ligand

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substitution reactions of the M2Cl62- anions. The electronic absorption spectra and vibrational spectra are interpreted. A normal coordinate analysis of the M2Cl62- anions are reported. Startling counterion effects in ligand substitution reactions in CH2Cl2 solvent were observed.

The transformation M-M → M-H-M+, in which a metal-metal bond is protonated by strong acid, has been studied in several organomettalic systems. Electronic spectra are tentatively interpreted in terms of three-center two-electron M-H-M bonding. The stretching vibrations associated with a W-H-W bridge are assigned. Infrared spectra indicate the presence of isomeric protonated species for several iron compounds. Base strength determination indicates that the replacement of Fe by Ru or replacement of CO by P(OCH3)3 both increase the basicity of [(π-C5H5)Fe(CO)2]2 by at least 2-3 orders of magnitude.

Ancillary chapters deal with the present state of π-cyclopropenium chemistry, predictions about the infrared spectra of π-cyclopropenium complexes and an original technique for graphical display of the con­centrations of the various species present during an acid-base titra­tion in acetic acid. A brief description of my advanced placement freshman chemistry course is included.

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):
  • Rossman, George Robert (advisor)
  • Gray, Harry B. (co-advisor)
Thesis Committee:
  • Unknown, Unknown
Defense Date:6 March 1973
Funding AgencyGrant Number
Record Number:CaltechTHESIS:10232017-110825526
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10535
Deposited By: Benjamin Perez
Deposited On:23 Oct 2017 22:42
Last Modified:20 Dec 2019 19:53

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