Rhenium nitrosyl complexes with simple and with sterically demanding aromatic thiolate ligands: X-ray crystal structures of [PPh4][Re2(SC6H4Me-4)7(NO)2]·CH2Cl2and [Re(SC6H3Pri2-2,6)4(NO)]

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Abstract
Reaction of [ReCl2(OMe)(NO)(PPh3)2] with a range of thiophenols under basic conditions gives one of two classes of products depending on the steric requirements of the thiols. A representative member of each class has been characterised by an X- ray crystal structure determination. Thiophenols with methyl or isopropyl groups in their ortho positions give the mononuclear complexes [Re(SR)4(NO)](SR = SC6H2Pri 3-2,4,6, SC6H3Pri 2-2,6, SC6H2Pri 2-2,6-4- Br, or SC6H2Me3-2,4,6) which are trigonal bipyramidal with an axial NO group. Thiophenols without ortho-substituents give the dinuclear anions [Re2(SR)7(NO)2]–(SR = SPh or SC6H4Me-4) which contain a triple thiolate bridge between two equivalent rhenium atoms. These anions show a fluxionality involving intramolecular exchange of six thiolato-ligands.