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Rhenium nitrosyl complexes with simple and with sterically demanding aromatic thiolate ligands: X-ray crystal structures of [PPh 4 ][Re 2 (SC 6 H 4 Me-4) 7 (NO) 2 ]·CH 2 Cl 2 and [Re(SC 6 H 3 Pr i 2 -2,6) 4 (NO)]

1985; Royal Society of Chemistry; Issue: 8 Linguagem: Inglês

10.1039/dt9850001533

2050-5671

Philip J. Blower, Jonathan R. Dilworth, John P. Hutchinson, Jon Zubieta,

Organometallic Compounds Synthesis and Characterization

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 = SC6H2Pri3-2,4,6, SC6H3Pri2-2,6, SC6H2Pri2-2,6-4- 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.