| 19303144 |
Song LC, Gai B, Wang HT, Hu QM: Synthesis, characterization and electrocatalysis of diiron propanediselenolate derivatives as the active site models of [FeFe]-hydrogenases. J Inorg Biochem. 2009 May;103(5):805-12. Epub 2009 Feb 15.
As an extension of our study on the H-cluster model compounds, a series of diiron propanediselenolate (PDS)-type models have been successfully synthesized. Reaction of diselenol HSe (CH (2))(3) SeH with Fe (3)(CO)(12) in THF (tetrahydrofuran) at reflux gave the parent model compound [micro-Se (CH (2))(3) Se-micro] Fe (2)(CO)(6) (1) in 48% yield. Further reaction of 1 with PPh (3) or PPh (2) H in the presence of Me (3) NO in MeCN at room temperature afforded the phosphine-monosubstituted model compounds [micro-Se (CH (2))(3) Se-micro] Fe (2)(CO)(5)(L) (2, L=PPh (3); 3, L=PPh (2) H) in 76% and 68% yields, respectively. Similarly, the N-heterocyclic carbene I (Mes)-monosubstituted model compound [micro-Se (CH (2))(3) Se-micro] Fe (2)(CO)(5)(I (Mes)) (4) could be prepared in 46% yield by reaction of imidazolium salt I (Mes).HCl with n-BuLi followed by treatment of the resulting I (Mes) ligand with 1 in THF at room temperature. Compounds 1-4 were fully characterized by elemental analysis and various spectroscopic methods. While the structures of 1-4 were further confirmed by X-ray crystallography, the comparative study of 1 and its analog [micro-S (CH (2))(3) S-micro] Fe (2)(CO)(6) demonstrates that 1 is a better catalyst for TsOH proton reduction to hydrogen under electrochemical conditions. |
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