University of Illinois Urbana-Champaign

Photochemistry of cyclopentadienyliron(II) arene complexes and tetraorganoborate salts

Park, Kyung Mi

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Description

Title
Photochemistry of cyclopentadienyliron(II) arene complexes and tetraorganoborate salts
Author(s)
Park, Kyung Mi
Issue Date
1992
Doctoral Committee Chair(s)
Schuster, Gary B.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
  • Chemistry, Inorganic
  • Chemistry, Organic
Language
eng
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.
Type of Resource
text
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http://hdl.handle.net/2142/21652
Copyright and License Information
Copyright 1992 Park, Kyung Mi

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