Details
| Original language | English |
|---|---|
| Article number | e202200143 |
| Journal | European Journal of Inorganic Chemistry |
| Volume | 2022 |
| Issue number | 16 |
| Early online date | 25 Mar 2022 |
| Publication status | Published - 1 Jun 2022 |
Abstract
While the chemistry of ferrocene is rich and widely explored, this is not the case for the isoelectronic cobaltocenium cation. Here we report the first syntheses of triflate substituted cobaltocenium cations based on respective (cyclopentadienone)(cylopentadienyl)cobalt(I) complexes, which have first been reported by Vollhardt et al. ca. forty years ago. Reaction with triflic anhydride affords the triflate substituted cobaltocenium cations, which upon treatment with lithium diisopropylamide undergo the first anionic thia-Fries rearrangements of cobaltocenium complexes. To our knowledge, this is, in addition, the first case of a deprotonation of a cobaltocenium complex by a lithium base. Alternatively, desilylation of silyl derivatives with cesium fluoride caused anion formation leading to the rearrangement products in higher yields. The 2-(trifluoromethylsulfonyl)(cyclopentadienone) complexes obtained were fully characterized including a crystal structure analysis. As with ferrocene, respective mesylates or tosylates do not undergo the rearrangement.
Keywords
- Anionic thia-Fries rearrangement, Cobalt, Cobaltocenium, Cyclopentadienyl ligands, ortho Lithiation
ASJC Scopus subject areas
- Chemistry(all)
- Inorganic Chemistry
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In: European Journal of Inorganic Chemistry, Vol. 2022, No. 16, e202200143, 01.06.2022.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - The First Anionic Thia-Fries Rearrangement at the Cobaltocenium Cation
AU - Boston, Geanne M.R.
AU - Butenschön, Holger
N1 - Funding Information: We thank Dr. Gerald Dräger, Institut für Organische Chemie, Leibniz Universität Hannover, for performing the crystallographic measurement. Open Access funding enabled and organized by Projekt DEAL.
PY - 2022/6/1
Y1 - 2022/6/1
N2 - While the chemistry of ferrocene is rich and widely explored, this is not the case for the isoelectronic cobaltocenium cation. Here we report the first syntheses of triflate substituted cobaltocenium cations based on respective (cyclopentadienone)(cylopentadienyl)cobalt(I) complexes, which have first been reported by Vollhardt et al. ca. forty years ago. Reaction with triflic anhydride affords the triflate substituted cobaltocenium cations, which upon treatment with lithium diisopropylamide undergo the first anionic thia-Fries rearrangements of cobaltocenium complexes. To our knowledge, this is, in addition, the first case of a deprotonation of a cobaltocenium complex by a lithium base. Alternatively, desilylation of silyl derivatives with cesium fluoride caused anion formation leading to the rearrangement products in higher yields. The 2-(trifluoromethylsulfonyl)(cyclopentadienone) complexes obtained were fully characterized including a crystal structure analysis. As with ferrocene, respective mesylates or tosylates do not undergo the rearrangement.
AB - While the chemistry of ferrocene is rich and widely explored, this is not the case for the isoelectronic cobaltocenium cation. Here we report the first syntheses of triflate substituted cobaltocenium cations based on respective (cyclopentadienone)(cylopentadienyl)cobalt(I) complexes, which have first been reported by Vollhardt et al. ca. forty years ago. Reaction with triflic anhydride affords the triflate substituted cobaltocenium cations, which upon treatment with lithium diisopropylamide undergo the first anionic thia-Fries rearrangements of cobaltocenium complexes. To our knowledge, this is, in addition, the first case of a deprotonation of a cobaltocenium complex by a lithium base. Alternatively, desilylation of silyl derivatives with cesium fluoride caused anion formation leading to the rearrangement products in higher yields. The 2-(trifluoromethylsulfonyl)(cyclopentadienone) complexes obtained were fully characterized including a crystal structure analysis. As with ferrocene, respective mesylates or tosylates do not undergo the rearrangement.
KW - Anionic thia-Fries rearrangement
KW - Cobalt
KW - Cobaltocenium
KW - Cyclopentadienyl ligands
KW - ortho Lithiation
UR - http://www.scopus.com/inward/record.url?scp=85128819168&partnerID=8YFLogxK
U2 - 10.1002/ejic.202200143
DO - 10.1002/ejic.202200143
M3 - Article
AN - SCOPUS:85128819168
VL - 2022
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 16
M1 - e202200143
ER -