1‐D Polymeric Iron(II) Thiolato Complexes: Synthesis, Structure, and Properties of ∞1[Fe(SR)2] (R = Ph, Mes), ∞1[Fe(NH3)(SPh)(µ‐SPh)] and ∞1[(µ‐SPh)Fe(NH3)2(µ‐SPh)2Fe(µ‐SPh)

Abstract

The first examples of polymeric homoleptic iron(II) thiolato complexes ∞1[Fe(SPh)2] and ∞1[Fe(SMes)2] (Ph = phenyl = C6H5, Mes = mesityl = C6H2–2,4,6‐(CH3)3) have been both prepared by reaction of [{Fe(N(SiMe3)2)2}2] with four equivalents of HSR ( R = Ph, Mes). In the crystal the two compounds form one‐dimensional chains with bridging thiolato ligands comprising distinctly different Fe–S–Fe bridging angles namely 75.20–75.25° in ∞1[Fe(SPh)2] and 91.38° in ∞1[Fe(SMes)2]. Reaction of ∞1[Fe(SPh)2] with stoichiometric amounts of NH3, generated by reaction of HN(SiMe3)2 with CH3OH, resulted in the formation of the polymeric ammonia thiolato complexes ∞1[Fe(NH3)(SPh))(µ‐SPh)] and ∞1[(µ‐SPh)Fe(NH3)2(µ‐SPh)2Fe(µ‐SPh)], which crystallize in the form of two structural isomers comprising either one or two µ2‐bridging phenyl‐thiolato groups with a bridging angle of 102.96° and 81.79–83.52°, respectively. Magnetic measurements reveal that this bridging angle has a distinct influence on the antiferromagnetic exchange interactions of the unpaired electrons along the chains in the different compounds. UV‐vis‐NIR spectra indicate low lying d‐d transitions (< 10000 cm–1) for all complexes.