Synthesis, structural characterization and electrochemical studies of [Fe < inf > 2 < /inf > (μ-L)(CO) < inf > 6 < /inf > ] and [Fe < inf > 2 < /inf > (μ-L)(CO) < inf > 5 < /inf > (PPh < inf > 3 < /inf > )] (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

Abstract

The reaction of heterocyclic 1,2-ene-dithiol ligands, namely, pyrazine-2,3-dithiol (H2pydt), quinoxaline-2,3-dithiol (H 2qdt) 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. A further reaction of complexes 1, 2 and 3 with PPh3 in the presence of equimolar amount of decarbonylating agent Me3NO in CH3CN at room temperature resulted in the formation of unsymmetrical mono-PPh3-substituted model complexes [Fe2{μ-pydt}(CO) 5PPh3] (4), [Fe2{μ-qdt}(CO) 5PPh3] (5) and [Fe2{μ-ppdt}(CO) 5PPh3] (6), respectively. The complexes 1-6 were well characterized by routine elemental analysis, IR, 1H NMR, 13C NMR spectroscopy and unambiguously characterized by X-ray crystallographic analysis. IR spectroscopy and electrochemical analysis show that an increase of the electron- withdrawing character of the bridging ligands (where electron-withdrawing character is in the order of pydt2- > ppdt2- ≥ qdt2-) leads to a decreased electron density at the iron centers, which yield a milder reduction potential and higher CO stretching frequencies. All the compounds 1-6 are further characterized by electrochemical studies. © 2011 Elsevier B.V. All rights reserved.