Neue Synthesewege zu neutralen gemischtsubstituierten Eisen-Schwefel-Clustern / Novel Synthetic Pathways to Neutral Mixed-Ligand Iron-Sulfur Clusters

Abstract

The reaction of [Fe(NiSiMe 3 ) 2 ) 2 ] with thiols RSH, elemental sulfur, and neutral ligands L (with sulfur donor atoms, e. g. thiourea derivatives) gives [Fe 4 S 4 (SR) 2 L 2 ] clusters in high yields. The structure of [Fe 4 S 4 (2.4.6-(C 3 H 7 ) 3 C 6 H 2 -S) 2 (dpdmi) 2 ] (dpdmi: diisopropyldimethyl- imidazolthion) was determined by X-ray crystallography. When [Fe 4 S 4 I 4 ] 2- is reacted with a large excess of PMePh 2 or PMe 2 Ph [F 6 S 6 I 2 (PMePh 2 ) 4 ] and [Fe 6 S 6 l2(PMe 2 Ph) 4 ]. respectively, are obtained in nearly quantitative yield. Basket-like structures of the [Fe 6 S 6 ] 2+ cores were detected by X-ray structure analysis. While [Fe 4 S 4 (SR) 4 ] 2- clusters do not react with phosphanes at ambient temperature 2:2 functional­ized species like [Fe 4 S 4 (SR) 2 (tmtu) 2 ] lead to basket-type clusters [Fe 6 S 6 (SR) 2 (PR 3 ) 4 ].