(Spectro)electrochemical and Electrocatalytic Investigation of 1,1 '-Dithiolatoferrocene-Hexacarbonyldiiron

0505699 - ÚFCH JH 2020 RIV US eng J - Journal Article
Haessner, M. - Fiedler, Jan - Ringenberg, M. R.
(Spectro)electrochemical and Electrocatalytic Investigation of 1,1 '-Dithiolatoferrocene-Hexacarbonyldiiron.
Inorganic Chemistry. Roč. 58, č. 3 (2019), s. 1742-1745. ISSN 0020-1669. E-ISSN 1520-510X
Institutional support: RVO:61388955
Keywords : metal-metal bonds * proton-reduction * h-2 production * active-site * hydrogenase * models * complexes * carbonyl
OECD category: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)
Impact factor: 4.825, year: 2019
Method of publishing: Limited access

Hexacarbonyldiiron bridged by a 1,1'-dithiolatoferrocene, [Fe(C5H4S)(2){Fe(CO)(3)}(2)] (1), was synthesized, and the electrochemistry showed reversible oxidation at the Fe(C5H4S)(2) site and quasi-reversible reduction at the hexacarbonyldiiron site. Spectroelectro-chemical techniques showed reduction-induced ligand isomerization, where the thiolate ligand went from bridging to terminal and one carbon monoxide ligand moved to a quasi-bridging position. This mechanism was further supported by cyclic voltammetry simulation and density functional theory calculations. Complex 1 showed electrocatalytic activity toward hydrogen-evolving reaction.
Permanent Link: http://hdl.handle.net/11104/0297111