Reactions of Cluster Complex Triiron Enneacarbonyl Disulfide with Phosphine Ligands

Abstract

The cluster derivatives of the type [Fe3(μ3-S)2(CO)8L] or [Fe3(μ3-S)2(CO)7L] (L = phosphine ligands) have been prepared by carbonyl substitution reactions of [Fe3(μ3-S)2(CO)9] (A) with monophosphine PPh3 or diphosphine Ph2PCH2PPh2. Reaction of complex A with PPh3 in the presence of Me3NO·2H2O in MeCN afforded [Fe3(μ3-S)2(CO)8PPh3] (1) in 65% yield, whereas reaction of A with PPh3 at reflux in toluene gave 1 and [Fe3(μ3-S)2(CO)7(PPh3)2] (2) in 36% and 42% yields, respectively. However, complex [Fe3(μ3-S)2(CO)7(Ph2PCH2PPh2)] (3) could be prepared by two methods: (i) reaction of A with Ph2PCH2PPh2 in the presence of Me3NO·2H2O in MeCN in 54% yield; and (ii) reaction of A with Ph2PCH2PPh2 at reflux in toluene in 37% yield. The cluster complexes 1–3 were structurally characterized by elemental analysis, IR and NMR spectroscopic analysis. In addition, the molecular structures of 1 and 3 were determined by X-ray crystallography.[Supplemental materials are available for this article. Go to the publisher's online edition of Molecular Crystals and Liquid Crystals to view the free supplemental file.]