title: Selenium makes the difference: protonation of [FeFe]-hydrogenase mimics with diselenolato ligands.
abstract: The synthetic models of the active site of an [FeFe]-hydrogenase containing a Sn atom in the bridgehead of the diselenato ligand, namely [Fe2(CO)6{μ-(SeCH2Se)SnMe2}], 3 and [Fe2(CO)6{μ-(SeCH2)2SnMe2}], 4 have been synthesized and characterized by different spectroscopic methods. The protonation properties of complex 4 have been investigated by monitoring the IR spectra in the carbonyl stretching region,1H NMR in the hydride region as well as the77Se{H} NMR upon addition of strong and moderate acids wherein the protonation of the active site of the [FeFe]-hydrogenase at one of its internal basic sites is considered an essential step in the catalytic cycle. Furthermore, we investigated the redox properties and the catalytic behaviour of complexes 3 and 4 in the presence of AcOH as a source of protons suggesting an ECE (E = electrochemical process, C = chemical process) mechanism.
authors.affiliation: Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldt Str. 8, 07743 Jena, Germany. wolfgang.weigand@uni-jena.de.
authors.forename: Hassan
authors.identifier: http://orcid.org/0000-0003-2419-9782
authors.initials: H
authors.lastname: Abul-Futouh
authors.affiliation: Chemistry Department, Jordan University of Science and Technology, Irbid 22110, Jordan. kateeb@just.edu.jo.
authors.forename: Mohammad
authors.initials: M
authors.lastname: El-Khateeb
authors.affiliation: Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldt Str. 8, 07743 Jena, Germany. wolfgang.weigand@uni-jena.de.
authors.forename: Helmar
authors.initials: H
authors.lastname: Görls
authors.affiliation: Chemistry Department, Jordan University of Science and Technology, Irbid 22110, Jordan. kateeb@just.edu.jo.
authors.forename: Khalil Jamil
authors.initials: KJ
authors.lastname: Asali
authors.affiliation: Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldt Str. 8, 07743 Jena, Germany. wolfgang.weigand@uni-jena.de.
authors.forename: Wolfgang
authors.identifier: http://orcid.org/0000-0001-5177-1006
authors.initials: W
authors.lastname: Weigand
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D002384:Catalysis; D020134:Catalytic Domain; D004563:Electrochemistry; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D008024:Ligands; D011522:Protons; D012643:Selenium / Q000737:chemistry*
chemical_list: D008024:Ligands; D011522:Protons; D006864:Hydrogenase; D012643:Selenium