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 D. Hoff

doi:10.1021/ic025590b

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 D. Hoff

Chemistry

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

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 (US)
Pages (from-to)	3212-3217
Number of pages	6
Journal	Inorganic Chemistry
Volume	41
Issue number	12
DOIs	https://doi.org/10.1021/ic025590b
State	Published - Jun 17 2002

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Capps, K. B., Whitener, G. D., Bauer, A., Abboud, K. A., Wasser, I. M., Vollhardt, K. P. C., & Hoff, C. D. (2002). 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. Inorganic Chemistry, 41(12), 3212-3217. https://doi.org/10.1021/ic025590b

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 D.

In: Inorganic Chemistry, Vol. 41, No. 12, 17.06.2002, p. 3212-3217.

Research output: Contribution to journal › Article › peer-review

Capps, KB, Whitener, GD, Bauer, A, Abboud, KA, Wasser, IM, Vollhardt, KPC & Hoff, CD 2002, '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', Inorganic Chemistry, vol. 41, no. 12, pp. 3212-3217. https://doi.org/10.1021/ic025590b

Capps KB, Whitener GD, Bauer A, Abboud KA, Wasser IM, Vollhardt KPC et al. 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. Inorganic Chemistry. 2002 Jun 17;41(12):3212-3217. https://doi.org/10.1021/ic025590b

Capps, Kenneth B. ; Whitener, Glenn D. ; Bauer, Andreas ; Abboud, Khalil A. ; Wasser, Ian M. ; Vollhardt, K. Peter C. ; Hoff, Carl D. / 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. In: Inorganic Chemistry. 2002 ; Vol. 41, No. 12. pp. 3212-3217.

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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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