title: Synthesis and crystal structures of (fulvalene)W(2)(SH)(2)(CO)(6), (fulvalene)W(2)(mu-S(2))(CO)(6), and (fulvalene)W(2)(mu-S)(CO)(6): low valent tungsten carbonyl sulfide and disulfide complexes stabilized by the bridging fulvalene ligand.
abstract: Reaction of FvW(2)(H)(2)(CO)(6) with 2/8S(8) in THF results in rapid and quantitative formation of FvW(2)(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 FvW(2)(SH)(2)(CO)(6) (1) with PhN[double bond]NPh produces FvW(2)(mu-S(2))(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, FvW(2)(mu-S)(CO)(6) (3), which was analyzed crystallographically. The enthalpy of sulfur atom insertion into FvW(2)(H)(2)(CO)(6), yielding 1, has been measured by solution calorimetry.
authors.affiliation: Department of Chemistry, University of Miami, Coral Gables, Florida 33124, USA.
authors.forename: Kenneth B
authors.initials: KB
authors.lastname: Capps
authors.forename: Glenn D
authors.initials: GD
authors.lastname: Whitener
authors.forename: Andreas
authors.initials: A
authors.lastname: Bauer
authors.forename: Khalil A
authors.initials: KA
authors.lastname: Abboud
authors.forename: Ian M
authors.initials: IM
authors.lastname: Wasser
authors.forename: K Peter C
authors.initials: KP
authors.lastname: Vollhardt
authors.forename: Carl D
authors.initials: CD
authors.lastname: Hoff