Five-coordinate rhenium(III)-thiolato complexes: the structure of [Re(SCH 2PhOCH 3) 3(PPh 3) 2

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A novel five-coordinate rhenium(III)-thiolato complex, Re(SCH 2C 6H 4OCH 3- p) 3(PPh 3) 2 has been isolated during the reaction of trans-ReOCl 3(PPh 3) 2 with p-methoxybenzyl mercaptan. In the unexpected structure that was acquired, the central metal has undergone a reduction from Re(V) to Re(III). The five-coordinate Re(III) complex has been characterized by spectroscopic methods, elemental analysis and X-ray crystallography. X-ray crystallographic studies showed the coordination geometry around rhenium to be that of a trigonal bipyramid. The basal plane is defined by three sulfur atoms of the monodentate ligand, while the two apical positions are occupied by two phosphines of the precursor.