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Description
Title: | Structural and Functional Models of the Iron -Only Hydrogenase Enzymes |
Author(s): | Lawrence, Joshua D. |
Doctoral Committee Chair(s): | Rauchfuss, Thomas B. |
Department / Program: | Chemistry |
Discipline: | Chemistry |
Degree Granting Institution: | University of Illinois at Urbana-Champaign |
Degree: | Ph.D. |
Genre: | Dissertation |
Subject(s): | Chemistry, Biochemistry |
Abstract: | New structural models for the H2-oxidizing state of the H-cluster were synthesized. Electron-rich polyisocyano compounds Fe2(S 2CnH2n)(CO)2(CNMe)4 undergo oxidatively induced reaction with additional CNMe to give [Fe2(S2CnH 2n)(CNMe)7](PF6)2, the first members of a new class of iron thiolates. Crystallographic characterization established that the 34 e- dinuclear core resembles the [Fe 2]H portion of the H-cluster. Treatment of [Fe2(S 2C3H6)(CNMe)7](PF6) 2 with excess CNMe led to [Fe2(S2C3H 6)(CNMe)10](PF6)2; the rate of addition of isocyanide is increased by more than three orders of magnitude under photolytic conditions. |
Issue Date: | 2002 |
Type: | Text |
Language: | English |
Description: | 161 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2002. |
URI: | http://hdl.handle.net/2142/84070 |
Other Identifier(s): | (MiAaPQ)AAI3070020 |
Date Available in IDEALS: | 2015-09-25 |
Date Deposited: | 2002 |
This item appears in the following Collection(s)
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Dissertations and Theses - Chemistry
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Graduate Dissertations and Theses at Illinois
Graduate Theses and Dissertations at Illinois