Synthesis, structural characterization and electrochemical studies of [Fe2(μ-L)(CO)6] and [Fe2(μ-L)(CO)5(PPh3)] (L = pyrazine-2,3-dithiolate, quinoxaline-2,3-dithiolate and pyrido[2,3-b]pyrazine-2,3-dithiolate): Towards modeling the active site of[FeFe]–Hydrogenase

Synthesis, structural characterization and electrochemical studies of [Fe2(μ-L)(CO)6] and [Fe2(μ-L)(CO)5(PPh3)] (L = pyrazine-2,3-dithiolate, quinoxaline-2,3-dithiolate and pyrido[2,3-b]pyrazine-2,3-dithiolate): Towards modeling the active site of[FeFe]–Hydrogenase: Publication year: 2011
Source: Journal of Organometallic Chemistry, In Press, Accepted Manuscript, Available online 20 June 2011
Gummadi, Durgaprasad , Ramababu, Bolligarla , Samar K., Das
The reaction of heterocyclic 1,2-ene-dithiol ligands, namely, pyrazine-2,3-dithiol (H2pydt), quinoxaline-2,3-dithiol (H2qdt) and pyrido[2,3-b]pyrazine-2,3-dithiol (H2ppdt) with Fe2(CO)9 yields the ‘[FeFe]–hydrogenase’ model complexes [Fe2{μ-pydt}(CO)6] (1), [Fe2{μ-qdt}(CO)6] (2) and [Fe2{μ-ppdt}(CO)6] (3), respectively. Highlights: ► Reaction of heterocyclic 1,2-ene-dithiols with Fe2(CO)9 yields the title complexes. ► These compounds further react with PPh3 to form mono-PPh3-substituted derivatives. ► The system shows relatively low reduction potentials among related model compounds. ► Electro-catalytic hydrogen generation has been demonstrated.