Synthesis and characterization of two P,S,N-coordinated cis-dioxorhenium (V) complexes

In the course of our investigations into mixed ligand systems containing thiol residues, we have examined, among others, the reactions of bidentate aminethiols with monodentate thiols, as well as tridentate/monodentate mixed ligand systems in the presence of ReOCl3(PPh3)2. Mixed ligand complexes of the general type "2+1+1" and "3+1" have been isolated. Surprisingly, in our synthetic attempts to clarify the mechanism of such reactions, we revceived two unexpected cis-dioxorhenium(V) P,S,N-coordinated complexes, where the aminethiol acts as a bidentate ligand over the Re(V) precursor. The two novel complexes of the general formula ReO2[R2NCH2CH2S][PPh3] where NR2=NEt2 (Complex 1) and NR2=N(CH2CH2)2C(OCH2)2 (Complex 2) are presented below. Both complexes have been characterized by elemental analysis and spectroscopic methods. Crystallographic studies show that the coordination geometry around rhenium is trigonal bipyramidal with the two cis-oxo groups and the sulfur atom of the ligand occupying the basal plane, while the nitrogen of the ligand and the phosphorus occupy the apical positions.