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Title:Photochemistry of cyclopentadienyliron(II) arene complexes and tetraorganoborate salts
Author(s):Park, Kyung Mi
Doctoral Committee Chair(s):Schuster, Gary B.
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Inorganic
Chemistry, Organic
Abstract:The photodearylation mechanism of (CpFe(ArH)) $\sp{+}$X$\sp{-}$ was studied. Irradiation of either the free ion or the ion pair in solution containing benzonitrile (PhCN) leads to a loss of the arene ligand and formation of a tris-nitrile complex ( (CpFe(PhCN)$\sb3\rbrack\sp{+}$). Two important reactive intermediates are detected. One, formed from irradiation of the ion pair, is assigned as the ring-slipped $\eta\sp4$-arene-Cp-iron compound covalently bound to its counter ion. The other, formed from irradiation of freely solvated cation, is assigned as the coordinatively unsaturated ring-slipped $\eta\sp4$-arene-Cp-iron compound. Also, the photoreaction of (CpFe(ArH)) $\sp{+}$X$\sp{-}$ in solutions containing epoxides was investigated.
The di-$\pi$-borate rearrangement mechanism was studied by comparing the reactivities of phenyl- and methyl-substituted borates. Irradiation of these borates produces oxygen- and water-sensitive boron-containing three-membered ring compounds, and biradical anion is proposed as intermediate. Some of photolysis products are red or yellow, and the cause of this color was investigated.
Issue Date:1992
Type:Text
Language:English
URI:http://hdl.handle.net/2142/21652
Rights Information:Copyright 1992 Park, Kyung Mi
Date Available in IDEALS:2011-05-07
Identifier in Online Catalog:AAI9215863
OCLC Identifier:(UMI)AAI9215863


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