Spectroscopic and catalytic investigations of transition metal complexes intercalated in layered silicates
Nehmer, Warren Lee
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https://hdl.handle.net/2142/21547
Description
Title
Spectroscopic and catalytic investigations of transition metal complexes intercalated in layered silicates
Author(s)
Nehmer, Warren Lee
Issue Date
1989
Doctoral Committee Chair(s)
Hendrickson, David N.
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
Language
eng
Abstract
A battery of spectroscopic techniques, including electron paramagnetic resonance, $\sp{57}$Fe Mossbauer, UV-VIS, and magnetic susceptibility have been used in the study of layered silicates. The oxidative coupling of phenols catalyzed by copper complexes intercalated into smectite clay minerals show that this type of reaction can be made very selective, due to the environment of the interlamellar layer of the clay mineral. The oxidation of 2,6-dimethylphenol leads to a greater selectivity toward the diphenoquinone than the polyphenyleneoxide polymer when the catalytic reaction occurs in the clay inter-layer.
The intercalation of ferrocene and ferrocene dimers into clay minerals leads to mono-oxidized clay-metallocene complexes. When the metallocene is a species such as bis(fulvalene)diiron or biferrocene, the intercalated metallocene is mixed valent. The properties of the mixed valent metallocenes are similar to what is found in conventional salts. Exceptions to this are intercalated diferrocenylethane, which has not previously been isolated as a mixed valent salt, and bis(fulvalene)diiron in which the electron paramagnetic resonance signal is quite different from previously isolated salts.
The oxidation of structural iron in lepidomelane has also been investigated. An evaluation of the magnetic properties of a series of bromine-water oxidized samples has led to the conclusion that the oxidation of ferrous iron occurs from the edge of the clay crystal inward. This type of oxidation leads to highly oxidized samples that still have regions where the ferrous ions have not been oxidized.
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