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Title:Diferrous Structural and Functional Models of the Iron-Only Hydrogenases
Author(s):Boyke, Christine A.
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:Low temperature IR spectroscopic studies show that the protonation of (Et4N)2[Fe2(S2C3H 6)(CN)2(CO)4] with HOTs gave Et4N[Fe 2(S2C3H6)(CN)(CNH)(CO)4]. Et4N[Fe2(S2C3H6)(CN)(CNH)(CO) 4] undergoes an approximate first-order decay to the hydride, Et 4N[HFe2(S2C3H6)(CN) 2(CO)4]. Addition of a second equiv of H+ to Et4N[HFe2(S2C3H6)(CN) 2(CO)4] resulted in protonation at the CN-ligand to give [HFe2(S2C3H6)(CN)(CNH)(CO) 4. Decarbonylation of Et4N[HFe2(S2C 3H6)(CN)2(CO)4] in the presence of PPh3 resulted in Et4N[HFe2(S2C 3H6)(CN)2(CO)3(PPh3)] followed by Et4N[HFe2(S2C3H6)(CN) 2(CO)2(PPh3)2], which exist as multiple isomers. Photolysis of McCN solutions of Et4N[HFe2(S 2C3H6)(CN)2(CO)4] in the absence of PPh3 gave the solvolysis product, Et4N[HFe 2(S2C3H6)(CN)2(MeCN)(CO) 3]. Et4N[HFe2(S2C3H 6)(CN)2(MeCN)(CO)3] reacted with PMe3 and CN to produce (Et4N)[HFe2(S2C3H 6)(CN)2(PMe3)(CO)3] and (Et4N) 2[HFe2(S2C3H6)(CN) 3(CO)3].
Issue Date:2006
Type:Text
Language:English
Description:178 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2006.
URI:http://hdl.handle.net/2142/84217
Other Identifier(s):(MiAaPQ)AAI3223548
Date Available in IDEALS:2015-09-25
Date Deposited:2006


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