Selenium makes the difference: protonation of [FeFe]-hydrogenase mimics with diselenolato ligands12. Issue 9 (15th February 2017)

• Record Type: Journal Article
• Authors: Abul-Futouh, Hassan; El-khateeb, Mohammad; Görls, Helmar; Asali, Khalil Jamil; Weigand, Wolfgang
• Is Part Of: Dalton transactions. Volume 46:Issue 9(2017)
• Page Start: 2937
• Page End: 2947
• Publication Date: 2017-02-15
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt00057j
• Languages: English
• ISSNs: 1477-9226

Abstract

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-(SeCH2 Se)SnMe2 }], 3 and [Fe2 (CO)6 {μ-(SeCH2 )2 SnMe2 }], 4 have been synthesized and characterized by spectroscopic methods. 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-(SeCH2 Se)SnMe2 }], 3 and [Fe2 (CO)6 {μ-(SeCH2 )2 SnMe2 }], 4 have been synthesized and characterized by different spectroscopic methods. The protonation properties of complex4 have been investigated by monitoring the IR spectra in the carbonyl stretching region, 1 H NMR in the hydride region as well as the 77 Se{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 complexes3 and4 in the presence of AcOH as a source of protons suggesting an ECE (E = electrochemical process, C = chemical process) mechanism.