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)]. Issue 5 (28th January 2019)

• Record Type: Journal Article
• Authors: Eichhöfer, Andreas; Buth, Gernot
• Is Part Of: European journal of inorganic chemistry. Issue 5(2019)
• Page Start: 639
• Page End: 646
• Publication Date: 2019-01-28
• Subjects: Iron -- Sulfur -- Synthesis design -- Structure elucidation -- Magnetic properties; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201801178
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The first examples of polymeric homoleptic iron(II) thiolato complexes∞ 1 [Fe(SPh)2 ] and∞ 1 [Fe(SMes)2 ] (Ph = phenyl = C6 H5, Mes = mesityl = C6 H2– 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 CH3 OH, 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)2 Fe(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. Abstract : The paper presents the synthesis and structural characterization of polymeric iron(II) thiolate complexes, which are either homoleptic or additionally coordinated by ammonia, along with an investigation of their magnetic properties.