The reduction of the compound [Fe<inf>2</inf>(CO)<inf>4</inf>(κ <sup>2</sup>-dmpe)μ-(SCH<inf>2</inf>)<inf>2</inf>NBn] [dmpe = 1,2-bis(dimethylphosphino)ethane], which is considered as an Fe <sup>I</sup>-Fe<sup>I</sup> model of the [2Fe]<inf>H</inf> subsite of [Fe-Fe]H<inf>2</inf>ases with a rotated conformation in the solid state, was investigated by cyclic voltammetry. Under reductive conditions, [Fe <inf>2</inf>(CO)<inf>4</inf>(κ<sup>2</sup>-dmpe)μ-(SCH <inf>2</inf>)<inf>2</inf>NBn] undergoes electron-transfer-catalyzed isomerization to afford an isomer featuring a bridging diphosphine [Fe <inf>2</inf>(CO)<inf>4</inf>(μ-dmpe)μ-(SCH<inf>2</inf>)<inf>2</inf>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 <inf>2</inf>(CO)<inf>4</inf>(μ-dmpe)μ-(SCH<inf>2</inf>)<inf>2</inf>NBn]. The symmetrization of the coordination sphere results in the disruption of the agostic interaction that stabilized the rotated isomer

DE GIOIA, L., Elleouet, C., Munery, S., Pétillon, F., Schollhammer, P., Talarmin, J., et al. (2014). Reductive Behavior of [Fe2(CO)4(κ2-dmpe){μ-(SCH2)2NBn}]: Effect of Symmetrization on the Rotated Conformation in FeI-FeI Models of [2Fe]H Subsite of [Fe-Fe]­H2ases. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2014(22), 3456-3461 [10.1002/ejic.201402335].

Reductive Behavior of [Fe2(CO)4(κ2-dmpe){μ-(SCH2)2NBn}]: Effect of Symmetrization on the Rotated Conformation in FeI-FeI Models of [2Fe]H Subsite of [Fe-Fe]­H2ases

DE GIOIA, LUCA
Primo
;
ZAMPELLA, GIUSEPPE
Ultimo
2014

Abstract

The reduction of the compound [Fe2(CO)42-dmpe)μ-(SCH2)2NBn] [dmpe = 1,2-bis(dimethylphosphino)ethane], which is considered as an Fe I-FeI model of the [2Fe]H subsite of [Fe-Fe]H2ases with a rotated conformation in the solid state, was investigated by cyclic voltammetry. Under reductive conditions, [Fe 2(CO)42-dmpe)μ-(SCH 2)2NBn] undergoes electron-transfer-catalyzed isomerization to afford an isomer featuring a bridging diphosphine [Fe 2(CO)4(μ-dmpe)μ-(SCH2)2NBn]. 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(μ-dmpe)μ-(SCH2)2NBn]. The symmetrization of the coordination sphere results in the disruption of the agostic interaction that stabilized the rotated isomer
Articolo in rivista - Articolo scientifico
Bioinspired chemistry; Density functional calculations; Electrochemistry; Hydrogenases; Iron; Inorganic Chemistry
English
3456
3461
6
DE GIOIA, L., Elleouet, C., Munery, S., Pétillon, F., Schollhammer, P., Talarmin, J., et al. (2014). Reductive Behavior of [Fe2(CO)4(κ2-dmpe){μ-(SCH2)2NBn}]: Effect of Symmetrization on the Rotated Conformation in FeI-FeI Models of [2Fe]H Subsite of [Fe-Fe]­H2ases. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2014(22), 3456-3461 [10.1002/ejic.201402335].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/97047
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