High-valent iron compounds supported by pentadentate ligands
by Klinker, Eric James, Ph.D., UNIVERSITY OF MINNESOTA, 2007, 185 pages; 3289163

Abstract:

High-valent nonheme iron-oxo units are proposed as key oxidizing intermediates in many iron dependent oxygenases. The pursuit of catalytically relevant intermediates has attracted attention from inorganic chemists interested in generating small-molecule models of the enzyme active sites. In 2003, well characterized examples of synthetic nonheme oxoiron(IV) compounds appeared in the literature and opened the door for research in the area. The intent of this research is to generate and identify new oxoiron(IV) compounds and to explore their chemistry. By extension, isoelectronic imidoiron(IV) complexes have also been sought for study.

A new series of high-valent iron(IV) species supported by pentadentate N5 ligands has been prepared at room temperature. These systems provide remarkable solution state stability to the high-valent oxoiron(IV) compounds and moderate stability to the analogous imidoiron(IV) complexes. The solution stability of these compounds has allowed their extensive characterization. Examination of these species, which are supported by the same pentadentate ligands, allows for a direct comparison between high-valent iron compounds with different terminal groups.

The oxoiron(IV) compounds have shown impressive reactivity towards hydrocarbons. The discovery of oxidative chemistry is relevant to biological systems, as the results support the proposed role of oxoiron(IV) units as key oxidizing intermediates in enzyme catalytic cycles.

 
AdviserLawrence Que, Jr.
SchoolUNIVERSITY OF MINNESOTA
SourceDAI/B 68-11, p. , Feb 2008
Source TypeDissertation
SubjectsInorganic chemistry
Publication Number3289163
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