More Fun Than Anything

Author: Harris, Daniel Charles

Year: 1973

Degree: Dissertation (Ph.D.)

Advisors: Rossman, George Robert; Gray, Harry B.

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/XBQW-9V06

Abstract

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.

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