Synthesis and electrochemical characterization of a tridentate Schiff-base ligated Fe(II) complex. (16th August 2016)

• Record Type: Journal Article
• Authors: Martin, Daniel J.; McCarthy, Brian D.; Piro, Nicholas A.; Dempsey, Jillian L.
• Is Part Of: Polyhedron. Volume 114(2016)
• Page Start: 200
• Page End: 204
• Publication Date: 2016-08-16
• Subjects: Electrochemistry -- Redox -- Iron -- Coordination chemistry -- Electrochemical-initiated degradation; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2015.12.003
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Characterization of an Fe(II) complex reveals that it is structurally similar to an analogous Ni(II) species known to degrade to a H2 -evolving electrocatalytic film under reducing protic conditions. However, the Fe species degrades under purely reducing conditions and does not require a proton source. Abstract: The structural and electronic properties of an Fe(II) Schiff-base complex, [Fe(N2 S)2 ][ClO4 ]2 (N2 S = 2-pyridyl-N-(2′-methylthiophenyl)methylenimine), are described and compared to an analogous Ni(II) species known to degrade to a H2 -evolving electrocatalytic film. Although structurally similar, the two complexes exhibit stark differences in their electrochemical and optical properties, and decompose via different pathways under reducing potentials. At potentials negative of the Fe(II/I) reduction wave, the complex degrades to a species that weakly adsorbs to the electrode surface. Prolonged electrolysis leads to the deposition of an Fe-containing film on the electrode.