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

<div><p>Reactions of Fe₂(CO)₉ with thioacylhydrazones ArCH=NNHCSPh in THF afford Fe₂(CO)₆(μ-κ²S:κ²N-PhC(S)=NNCHArCHArN(CHAr)N=CSPh) (<b>1</b>, Ar = C₆H₅; <b>3</b>, Ar = 4-CH₃C₆H₄) and Fe(CO)₃(κ²S:N-PhC(=S)NHNCHArCHArN(CHAr)N=CSPh) (<b>2</b>, Ar = C₆H₅; <b>4</b>, 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.</p>