Structural and Functional Models of the Iron -Only Hydrogenase Enzymes

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Lawrence, Joshua D.

Contributors dc:contributor

• Rauchfuss, Thomas B.

• Chemistry, Biochemistry

Language dc:language

eng

Identifier

(MiAaPQ)AAI3070020

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84070