Syntheses, crystal structures, and electrochemistry of novel Fe₂SN and FeSN carbonyl complexes with pendant bases

Abstract

Reactions of Fe₂(CO)₉ with thioacylhydrazones ArCH=NNHCSPh in THF afford Fe₂(CO)₆(μ-κ²S:κ²N-PhC(S)=NNCHArCHArN(CHAr)N=CSPh) (1, Ar = C₆H₅; 3, Ar = 4-CH₃C₆H₄) and Fe(CO)₃(κ²S:N-PhC(=S)NHNCHArCHArN(CHAr)N=CSPh) (2, Ar = C₆H₅; 4, Ar = 4-CH₃C₆H₄). They have been characterized by elemental analyses, IR, ¹H NMR, and ¹³C NMR and structurally determined by X-ray crystallography. Electrochemical studies reveal that when using HOAc as a proton source, they exhibit high catalytic H₂-production.

Graphical abstract

Keywords:

• Hydrogenase
• Carbonyl iron
• Thio-Schiff base
• Cyclic voltammetry
• H₂ evolution

Supplementary material

CCDC 983053 (1), 1043668 (2), 983054 (3) and 1043669 (4) contain the supplementary crystallographic data (including structure factors) for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Supplemental data

Supplementary data including IR, NMR and CV data for this article can be accessed at http://dx.doi.org/10.1080/00958972.2015.1062479.

Disclosure statement

The authors declare no competing financial interest.

Additional information

Funding

This work was supported by the Mao Zedong Foundation of China; Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD); Natural Science Foundation of China [grant number 20572091]; Natural Science Foundation of Jiangsu Province [grant number 05KJB150151].