Effect of electron-withdrawing dithiolate bridge on the electron-transfer steps in diiron molecules related to [2Fe](H) subsite of the [FeFe]-hydrogenases.
Two hexacarbonyl diiron compounds featuring dithiolate bridges with strong electron-withdrawing groups (CO(2)Me, tetrachloro-biphenyl) were synthesized and structurally characterized. Electrochemical study of these compounds demonstrates that such electron-withdrawing groups have a pronounced effect on both the reduction potentials and the electron transfer process. The reduced forms of these compounds catalyze the reduction of protons in dichloromethane. However, the tetrachloro-biphenyl derivative is the only one able to work in the potential range of its primary reduction process. A catalytic reaction scheme is proposed.
Charreteur
Kévin
K
Université Européenne de Bretagne, 29238 Brest, France.
Kdider
Mohamed
M
Capon
Jean-François
JF
Gloaguen
Frédéric
F
Pétillon
François Y
FY
Schollhammer
Philippe
P
Talarmin
Jean
J
D002384:Catalysis; D004563:Electrochemistry; D004579:Electron Transport; D006864:Hydrogenase / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D011522:Protons; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D007506:Iron-Sulfur Proteins; D011522:Protons; D013438:Sulfhydryl Compounds; D007501:Iron; C118830:iron hydrogenase; D006864:Hydrogenase