[FeFe]-Hydrogenase H-Cluster Mimics with Unique Planar μ-(SCH 2 ) 2 ER 2 Linkers (E=Ge and Sn)

Hassan Abul-Futouh; Laith R. Almazahreh; Takahiro Sakamoto; Nhu Y. T. Stessman; Dennis L. Lichtenberger; Richard S. Glass; Helmar Görls; Philippe Schollhammer; Mohammad El-Khateeb; Grzegorz Mloston; Wolfgang Weigand

doi:10.1002/chem.201603843

[FeFe]-Hydrogenase H-Cluster Mimics with Unique Planar μ-(SCH 2 ) 2 ER 2 Linkers (E=Ge and Sn)

Hassan Abul-Futouh ¹ Laith R. Almazahreh ¹ Takahiro Sakamoto ² Nhu Y. T. Stessman ² Dennis L. Lichtenberger ² Richard S. Glass ² Helmar Görls ¹ Philippe Schollhammer ³ Mohammad El-Khateeb ⁴ Grzegorz Mloston ⁵ Wolfgang Weigand ¹

1 Friedrich-Schiller-Universität Jena

2 Department of Chemistry and Biochemistry [Tucson]

3 CEMCA - Chimie, Electrochimie Moléculaires et Chimie Analytique

4 Jordan University of Science and Technology

5 Łódź University of Technology

Abstract : Analogues of the [2Fe-2S] subcluster of hydrogenase enzymes in which the central group of the three-atom chain linker between the sulfur atoms is replaced by GeR2 and SnR2 groups are studied. The six-membered FeSCECS rings in these complexes (E=Ge or Sn) adopt an unusual conformation with nearly co-planar SCECS atoms perpendicular to the Fe-Fe core. Computational modelling traces this result to the steric interaction of the Me groups with the axial carbonyls of the Fe2(CO)6 cluster and low torsional strain for GeMe2 and SnMe2 moieties owing to the long C−Ge and C−Sn bonds. Gas-phase photoelectron spectroscopy of these complexes shows a shift of ionization potentials to lower energies with substantial sulfur orbital character and, as supported by the computations, an increase in sulfur character in the predominantly metal–metal bonding HOMO. Cyclic voltammetry reveals that the complexes follow an ECE-type reduction mechanism (E=electron transfer and C=chemical process) in the absence of acid and catalysis of proton reduction in the presence of acid. Two cyclic tetranuclear complexes featuring the sulfur atoms of two Fe2S2(CO)6 cores bridged by CH2SnR2CH2, R=Me, Ph, linkers were also obtained and characterized.

Keywords : sulfur photoelectron conformational analysis density functional calculations electrocatalysis

Type de document :

Article dans une revue

Chemistry - A European Journal, Wiley-VCH Verlag, 2017, 23 (2), pp.346 - 359. 〈10.1002/chem.201603843〉

Domaine :

Chimie / Chimie inorganique

Chimie / Chimie de coordination

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[FeFe]-Hydrogenase H-Cluster Mimics with Unique Planar μ-(SCH 2 ) 2 ER 2 Linkers (E=Ge and Sn)

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