Diferrous structural and functional models of the iron-only hydrogenases.
- Resource Type
- Theses
- Authors
- Boyke, Christine A.
- Source
- Dissertation Abstracts International; Dissertation Abstract International; 67-07B.
- Subject
- Chemistry, Inorganic
- Language
- English
Summary: 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].