University of Illinois Urbana-Champaign

Synthesis and Coordination Complexes of Bis-Pocket Siloxyporphyrins

Fang, Ming

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Description

Title
Synthesis and Coordination Complexes of Bis-Pocket Siloxyporphyrins
Author(s)
Fang, Ming
Issue Date
2008
Doctoral Committee Chair(s)
Kenneth S. Suslick
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 high yield synthetic route for an alkylthiolate-tailed bis-face protected iron porphyrin was developed. The high stability of this compound is likely due to the protection from the siloxy pocket around the thiolate tail. Very similar rhombic, high spin EPR spectra for this model compound and the P450 enzyme showed that the choice of a more basic thiolate tail is essential for model compounds to reproduce the electronic structure of the heme in P450. The single crystal x-ray structure showed that the sulfur atom is bound to the iron. The Fe-S bond distance is 2.237(7) A, and the iron is pulled out of the porphyrin plane by 0.50 A, indicating that the iron is in the high spin state. This Fe-S bond distance is very similar to the value reported for the P450 enzyme at its resting state. This is the first single crystal x-ray structure of a high spin alkylthiolate-tailed ferric porphyrin. UV-Vis and EPR spectroscopy also showed that methanol binding at low temperatures can induce the high spin to low spin transition for the thiolate-ligated iron porphyrin.
Graduation Semester
2008
Type of Resource
text
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http://hdl.handle.net/2142/84309

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