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

Kenneth B. Capps, Glenn D. Whitener, Andreas Bauer, Khalil A. Abboud, Ian M. Wasser, K. Peter C Vollhardt, Carl Hoff

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)3212-3217
Number of pages6
JournalInorganic Chemistry
Volume41
Issue number12
DOIs
StatePublished - Jun 17 2002

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Tungsten
disulfides
Carbon Monoxide
Disulfides
sulfides
tungsten
Crystal structure
Ligands
ligands
crystal structure
synthesis
atoms
insertion
sulfur
heat measurement
enthalpy
products
configurations
crystals
Atoms

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 journalArticle

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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.",
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AU - Bauer, Andreas

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AU - Wasser, Ian M.

AU - Vollhardt, K. Peter C

AU - Hoff, Carl

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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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