Synthesis and characterization of carbonyl thiolato [Et4N][M(CO)5SR] and [Et4N]2[M2(CO)8(SR)2] complexes (M = chromium, molybdenum, tungsten). Ligand substitution reactions and x-ray crystal structure of [Et4N]2[W2(CO)8(SPh)2] Academic Article uri icon


  • A series of complexes, [Et4N][M(CO)5SR] (M = Cr, Mo, W; R = H, Ph), have been synthesized and characterized by 1H and 13C NMR and IR spectroscopies. Gentle heating causes these complexes to lose a carbonyl ligand, yielding the doubly bridged sulfur dimers M2(CO)8(μ-SR)22-. The X-ray crystal structure of [Et4N]2[W2(CO)8(SPh)2] has been determined. The complex crystallizes in the triclinic space group P̅1 with unit cell parameters a = 9.8664 (17) Å, b = 9.8566 (22) Å, c = 11.8270 (26) Å, α = 65.790 (16)°, β = 81.710 (16)°, γ = 82.000 (16)°, V = 1034.0 (4) Å3, and Z = 1. Both mono- and dinuclear metal complexes readily react with phosphorus donor ligands to afford the carbon monoxide substituted complexes cis-M(CO)4(P)(SR)- (P = PMe3, P(OMe)3, PPh3). In addition, the dimers react with 1 atm of carbon monoxide to re-form the mononuclear species M(CO)5SR- in quantitative yields. Unsuccessful attempts to insert CO2, COS, or CS2 into the M-SR bond in the M(CO)5SR- derivatives are noted. © 1988, American Chemical Society. All rights reserved.

author list (cited authors)

  • Darensbourg, D. J., Sanchez, K. M., & Reibenspies, J.

citation count

  • 27

publication date

  • October 1988