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) angstrom from Fe with angle H-FE-S = 89(4)degrees. (PhS)Fe(H)(CO)2(P(OPh)3)2 crystallized in the monoclinic space group P2(1)/n with a = 9.935(2) angstrom, b = 36.185(5) angstrom, c = 12.112(2) angstrom, beta = 113.42(1)degrees, V = 3995.5(0) angstrom, 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+.