REACTIONS OF THE SH-GROUPS AND S2-GROUPS IN W(CO)5(SH)- AND MU-S[W(CO)5]22-

The mononuclear W(CO)5(SH)- and SH- bridged binuclear µ-HS[W(CO)5]2- complexes have been prepared by reaction of SH- with W(CO)6-The W(CO)5(SH)- complex reacts with acetic anhydride and 2,4-dinitrophenyl acetate to give the thioacetate complex, MeC(=0)SW(C0)5-. The reactivity of the SH- group is also demonstrated by the reaction of this complex with aliphatic ketones and aromatic aldehydes to yield thioketone, W(CO)5(S=CR2), and thioaldehyde, (ArCHS)W(CO)5, complexes of these otherwise unstable organic molecules. While the SH- group in µ-HS[W(CO)5]2- is considerably less reactive, deprotonation with strong base gives an S2--bridged dimer, µ-S[W(CO)5]22-, which readily reacts with halo compounds, E-Cl, to give the corresponding sulfur-bridged complexes, µ-E-S[W(CO)5]22-, where E = MesSn, MeHg, MeC(=0), PhCH2, or PH2P. All of the new compounds have been characterized spectroscopically. © 1979, American Chemical Society. All rights reserved.