Synthesis and Characterization of a Stable Iron(II) Hydride-Thiolate Complex: (PhS)Fe(H)(CO)2(P(OPh)3)2 Academic Article uri icon


  • The anionic, bis(phosphite)iron hydride complex [Et4N] [HFe(CO)2(P(OPh)3)2] reacts with aryl disulfides to yield simple, monofunctional iron thiolate anions, (ArS)Fe(CO)2(P(OPh)3)2- (Ar = Ph, Tol). Methylation of the thiolates resulted in the formation of thioether species (ArSMe)Fe(CO)2(P(OPh)3)2, while protonation resulted in the formation of the stable thiolate-hydride complexes (ArS)Fe(H)(CO)2(P(OPh)3)2. cct-(PhS)Fe(H)(CO)2(P(OPh)3)2 was characterized by X-ray diffraction and found to be a regular octahedral complex in which the phosphite ligands are trans and the carbonyls cis, mutually trans to the hydride and benzenethiolate ligands. The hydride was located 1.41(7) Å from Fe with ∠H-Fe-S = 89(4)°. (PhS)Fe(H)(CO)2(P(OPh)3)2 crystallized in the monoclinic space group P21/n with a = 9.935(2) Å, b = 36.185(5) Å, c = 12.112(2) Å, β= 113.42(1)°, V = 3995.5(0) Å,3 and Z = 4. (PhS)Fe(H)(CO)2(P(OPh)3)2 was protonated to form the novel thiol-hydride complex (PhSH)Fe(H)(CO)2-(P(OPh)3)2+. © 1994, American Chemical Society. All rights reserved.

author list (cited authors)

  • Wander, S. A., Reibenspies, J. H., Kim, J. S., & Darensbourg, M. Y.

citation count

  • 19

publication date

  • March 1994