Reaction of FvW2(H)2(CO)6 with 2/8S8 in THF results in rapid and quantitative formation of FvW2(SH)2(CO)6. The crystal structure of this complex is reported and shows that the two tungsten-hydrosulfide groups are on opposite faces of the fulvalene ligand in an anti configuration. Nevertheless, treatment of FvW2(SH)2(CO)6 (1) with PhN= NPh produces FvW2(μ-S2)(CO)6 (2) and Ph(H)NN(H)Ph. The crystal structure of the bridging disulfide, which cocrystallizes with 1 in a 2:1 ratio, is also described. Exposure of 2 equiv of ·CrCp*(CO)3 to 1 effects similar H atom transfers yielding 2 HCrCp*(CO)3 and 2. Attempts to obtain crystals of the latter from solutions derived from this reaction mixture furnished a third product, FvW2(μ-S)(CO)6 (3), which was analyzed crystallographically. The enthalpy of sulfur atom insertion into FvW2(H)2(CO)6, yielding 1, has been measured by solution calorimetry.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry