Novel hetero trinuclear complexes triply bridged by carbon disulphide; X-ray crystal structure of the complex [(OC)2(η5-C5H5)FeC(
S)SFe(η5-C5H5)(CO)2W(CO)5]
Abstract
The reaction between the metallodithioester–metal complexes [(OC)2(cp)FeC(S)SM(Ln)][M(Ln)= Fe(cp)(CO)2 or Re(CO)5; cp =η5-C5H5] and [M′(CO)5(thf)](M′= Cr, Mo, or W) or [Mn(cp)(CO)2(thf)](thf = tetrahydrofuran) produces in good yield stable heterotrinuclear complexes [(OC)2(cp)FeC(
[graphic omitted]′(CO)5] and [(OC)2(cp)FeC(
[graphic omitted]n(cp)(CO)2] in which the CS2 group is triply bridging. All these novel complexes have been characterized by elemental analyses, i.r., and 1H n.m.r. spectra. The µ3-CS2 derivatives readily decompose in solution to produce dithiocarboxylatometal complexes [(OC)2(cp)FeC(
[graphic omitted](Ln)][M(Ln)= Fe(cp)(CO) or Re(CO)4] and [M(CO)6](M = Cr, Mo, or W) or [Mn(cp)(CO)3], suggesting that the attachment of a metal atom to the unco-ordinated sulphur atom in the unit FeC(
S)SM does not labilize the carbon–sulphur bonds of the CS2 molecule. The structure of the triply bridged complex [(OC)2(η5-C5H5)FeC(
[graphic omitted](CO)5] has been determined by X-ray crystallography. The complex crystallizes in the triclinic space group P
with a= 6.647(1), b= 12.145(2), c= 14.795(2)Å, α= 82.33(1), β= 85.73(1), γ= 79.73(1)°, and Z= 2. 3 487 Reflection intensities with I > 3σ(I) led to R 0.024. The molecule is asymmetrical and contains a bent CS2 unit in which the carbon and sulphur atoms are trigonally hybridized and are σ-bonded to two Fe(η5-C5H5)(CO)2 and one W(CO)5 fragments. Relevant bond parameters are S–C–S 119.2(2)°, C–S 1.69(2), Fe–C 1.975(4), Fe–S 2.273(1), and W–S 2.563(1)Å.