ORGANOMETALLIC MODELS FOR THE HYDRODESULPHURISATION (HDS) REACTION: SYNTHESIS OF + (M = Rh, Ir) AND X-RAY STRUCTURE OF THE Rh DERIVATIVE, THE FIRST EXAMPLE OF A FULLY CHARACTERISED ?-THIOPHENE COMPLEX OF AN HDS ACTIVE METAL

Article abstract of DOI:10.1016/0022-328X(86)80512-5

Hydrogenation of <(NBD)M(PPh3)2> (M = Rh, Ir; NBD = norbornadiene) in CH2CL2/thiophene gives <(η-thiophene M(PPh3)2>⁺ (R = Rh, Ir) compounds, which have been isolated and characterised.In the case of <(η-thiophene)-Rh(PPh3)2>⁺ the structure has been determined by X-ray diffraction; the cation involves a trigonal arrangement of two phosphines and a ?-bonded thiophene around the Rh atom.Crystal data: triclinic, space group P1<*>, a 11.774(6), b 18.083(8), c 11.425(5) Angstroem, α 75.24(2), β 105.48(2), γ 103.24(2) deg., U 2227(2) Angstroem³, and Z = 2.The coordinated thiophene is readily displaced by donor ligands from the Rh complex, but is strongly bound in the Ir analog.