Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 22, Pages 3456-3461Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201402335
Keywords
Iron; Hydrogenases; Bioinspired chemistry; Electrochemistry; Density functional calculations
Categories
Funding
- Centre National de la Recherche Scientifique (CNRS)
- Universite de Bretagne Occidentale (UBO)
- University of Milano-Bicocca
Ask authors/readers for more resources
The reduction of the compound [Fe-2(CO)(4)((2)-dmpe){-(SCH2)(2)NBn}] [dmpe = 1,2-bis(dimethylphosphino)ethane], which is considered as an Fe-I-Fe-I model of the [2Fe](H) subsite of [Fe-Fe]H(2)ases with a rotated conformation in the solid state, was investigated by cyclic voltammetry. Under reductive conditions, [Fe-2(CO)(4)((2)-dmpe){-(SCH2)(2)NBn}] undergoes electron-transfer-catalyzed isomerization to afford an isomer featuring a bridging diphosphine [Fe-2(CO)(4)(-dmpe){-(SCH2)(2)NBn}]. Comparison of the crystallographic structures of the two isomers affords unique and direct experimental evidence that dissymmetrical coordination of the chelate ligand is required to promote the rotated conformation at one iron atom in this compound. DFT calculations were performed to rationalize this isomerization process and the slightly distorted structure of [Fe-2(CO)(4)(-dmpe){-(SCH2)(2)NBn}]. The symmetrization of the coordination sphere results in the disruption of the agostic interaction that stabilized the rotated isomer.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available