Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 3212-3217 |
| Number of pages | 6 |
| Journal | Inorganic Chemistry |
| Volume | 41 |
| Issue number | 12 |
| DOIs | |
| State | Published - Jun 17 2002 |
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ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
Synthesis and crystal structures of (fulvalene)W2(SH)2(CO)6, (fulvalene)W2(μ-S2)(CO)6, and (fulvalene)W2(μ-S)(CO)6 : Low valent tungsten carbonyl sulfide and disulfide complexes stabilized by the briging fulvalene ligand. / Capps, Kenneth B.; Whitener, Glenn D.; Bauer, Andreas; Abboud, Khalil A.; Wasser, Ian M.; Vollhardt, K. Peter C; Hoff, Carl.
In: Inorganic Chemistry, Vol. 41, No. 12, 17.06.2002, p. 3212-3217.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Synthesis and crystal structures of (fulvalene)W2(SH)2(CO)6, (fulvalene)W2(μ-S2)(CO)6, and (fulvalene)W2(μ-S)(CO)6
T2 - Low valent tungsten carbonyl sulfide and disulfide complexes stabilized by the briging fulvalene ligand
AU - Capps, Kenneth B.
AU - Whitener, Glenn D.
AU - Bauer, Andreas
AU - Abboud, Khalil A.
AU - Wasser, Ian M.
AU - Vollhardt, K. Peter C
AU - Hoff, Carl
PY - 2002/6/17
Y1 - 2002/6/17
N2 - 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.
AB - 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.
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U2 - 10.1021/ic025590b
DO - 10.1021/ic025590b
M3 - Article
VL - 41
SP - 3212
EP - 3217
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 12
ER -