1‐D Polymeric Iron(II) Thiolato Complexes: Synthesis, Structure, and Properties of ∞ 1 [Fe(SR) 2 ] (R = Ph, Mes), ∞ 1 [Fe(NH 3 )(SPh)(µ‐SPh)] and ∞ 1 [(µ‐SPh)Fe(NH 3 ) 2 (µ‐SPh) 2 Fe(µ‐SPh)]

The first examples of polymeric homoleptic iron(II) thiolato complexes ∞ 1 [Fe(SPh) 2 ] and ∞ 1 [Fe(SMes) 2 ] (Ph = phenyl = C 6 H 5 , Mes = mesityl = C 6 H 2– 2,4,6‐(CH 3 ) 3 ) have been both prepared by reaction of [{Fe(N(SiMe 3 ) 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 NH 3 , generated by reaction of HN(SiMe 3 ) 2 with CH 3 OH, resulted in the formation of the polymeric ammonia thiolato complexes ∞ 1 [Fe(NH 3 )(SPh))(µ‐SPh)] and ∞ 1 [(µ‐SPh)Fe(NH 3 ) 2 (µ‐SPh) 2 Fe(µ‐SPh)], which crystallize in the form of two structural isomers comprising either one or two µ 2 ‐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.