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Thomas Rauchfuss Whaley, Curtis 2015-09-25T22:14:03Z 2015-09-25T22:14:03Z 10000-01-01 2009 2009 While previous hydride-containing [FeFe]-hydrogenase models featured only bridging hydrides, we sought to prepare complexes of terminal hydrides that would be more relevant to mimicking this hydrogenase. Di-subferrous precursors, such as Fe2(S2C2H4)(CO)4 (PMe3)2, have been known for decades---well before the elucidation of the structure of the active site. Two-electron oxidation of Fe2(S2C2H4)(CO)4(PMe 3)2 in the presence of excess PMe3 in MeCN resulted in the formation of the diferrous [Fe2(S2C2H 4)(mu-CO)(NCMe)(CO)(PMe3)4](PF 6)2. This complex, when treated with hydride sources such as BH4- or AlH4- at low temperature, generated the first terminal hydride-containing [FeFe]-hydrogenase model complex, [HFe2(S2C2H4)(mu-CO)(CO)(PMe 3)4]PF6. This complex readily protonates with strong acids in MeCN to evolve H2 and regenerate the precursor MeCN-complex. The terminal hydride complex is thermally unstable, isomerizing to give an inert bridging hydride, even in the solid state. Made available in DSpace on 2015-09-25T22:14:03Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3395535.pdf: 1737126 bytes, checksum: 30406d1625c364b8829731341774d40f (MD5) Previous issue date: 2009 Embargo set by: Seth Robbins for item 85631 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 154 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2009. http://hdl.handle.net/2142/84350 (MiAaPQ)AAI3395535 eng Chemistry, Inorganic Modeling the Active Sites of [nickel-Iron]- and [iron-Iron]-Hydrogenases text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.