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(L_n)][M(L_n)= 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](L_n)][M(L_n)= 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.