University of Illinois Urbana-Champaign

Structural and Functional Models of the Iron -Only Hydrogenase Enzymes

Lawrence, Joshua D.

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Description

Title
Structural and Functional Models of the Iron -Only Hydrogenase Enzymes
Author(s)
Lawrence, Joshua D.
Issue Date
2002
Doctoral Committee Chair(s)
Rauchfuss, Thomas 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, Biochemistry
Language
eng
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.
Graduation Semester
2002
Type of Resource
text
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http://hdl.handle.net/2142/84070

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