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Title:Hydrogen Production From Model Complexes of the [iron-Iron]- and [nickel-Iron]-Hydrogenase Active Sites
Author(s):Barton, Bryan E.
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, Inorganic
Abstract:Unlike the [FeFe]-hydrogenases, model complexes for the [NiFe]-hydrogenases were unknown prior to the crystal structure in 1996. However, most synthetic efforts focused on structural models for the active site, and neglected the catalytically imperative hydride ligand. Thus, we sought a nickel-iron hydride complex to explore the relevant reactivity of the first (mu-H)Ni(mu-SR) 2Fe complex. We found that the previously reported (dppe)Ni(mu-pdt)Fe(CO) 3, a Ni(I)Fe(I) complex, reacted with acid to provide [(dppe)Ni(mu-H)(mu-pdt)Fe(CO) 3]+, the first nickel-iron hydride. After protonation, the hydride complex is amenable to substitution chemistry at the Fe(CO) 3 subunit. Further derivatives altering the Ni(diphosphine)(SR) 2 subunit have been achieved through an alternative synthetic procedure to the Ni(I)Fe(I) complex. All nickel-iron hydrides investigated are active catalysts for the reduction of protons. As the catalytic mechanism of [NiFe]-hydrogenase is widely speculative, the reactivity of this new class of nickel-iron hydrides offers powerful insights into Nature's catalytic mechanism. (Abstract shortened by UMI.).
Issue Date:2010
Type:Text
Language:English
Description:273 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2010.
URI:http://hdl.handle.net/2142/84354
Other Identifier(s):(MiAaPQ)AAI3455686
Date Available in IDEALS:2015-09-25
Date Deposited:2010


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