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)]

The first examples of polymeric homoleptic iron(II) thiolato complexes (1)(infinity)[Fe(SPh)(2)] and (1)(infinity)[Fe(SMes)(2)] (Ph = phenyl = C6H5, Mes = mesityl = C(6)H(2-)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 degrees in (1)(infinity)[Fe(SPh)(2)] and 91.38 degrees in (1)(infinity)[Fe(SMes)(2)]. Reaction of (1)(infinity)[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)(infinity)[Fe(NH3)(SPh))(mu-SPh)] and (1)(infinity)[(mu-SPh)Fe(NH3)(2)(mu-SPh)(2)Fe(mu-SPh)], which crystallize in the form of two structural isomers comprising either one or two mu(2)-bridging phenyl-thiolato groups with a bridging angle of 102.96 degrees and 81.79-83.52 degrees, 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.