The First Anionic Thia-Fries Rearrangement at the Cobaltocenium Cation

Research output: Contribution to journalArticleResearchpeer review

Authors

Research Organisations

View graph of relations

Details

Original languageEnglish
Article numbere202200143
JournalEuropean Journal of Inorganic Chemistry
Volume2022
Issue number16
Early online date25 Mar 2022
Publication statusPublished - 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

Cite this

The First Anionic Thia-Fries Rearrangement at the Cobaltocenium Cation. / Boston, Geanne M.R.; Butenschön, Holger.
In: European Journal of Inorganic Chemistry, Vol. 2022, No. 16, e202200143, 01.06.2022.

Research output: Contribution to journalArticleResearchpeer review

Boston GMR, Butenschön H. The First Anionic Thia-Fries Rearrangement at the Cobaltocenium Cation. European Journal of Inorganic Chemistry. 2022 Jun 1;2022(16):e202200143. Epub 2022 Mar 25. doi: 10.1002/ejic.202200143
Download
@article{6f1a390caaf34497bdf503dafaa12550,
title = "The First Anionic Thia-Fries Rearrangement at the Cobaltocenium Cation",
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",
author = "Boston, {Geanne M.R.} and Holger Butensch{\"o}n",
note = "Funding Information: We thank Dr. Gerald Dr{\"a}ger, Institut f{\"u}r Organische Chemie, Leibniz Universit{\"a}t Hannover, for performing the crystallographic measurement. Open Access funding enabled and organized by Projekt DEAL. ",
year = "2022",
month = jun,
day = "1",
doi = "10.1002/ejic.202200143",
language = "English",
volume = "2022",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag",
number = "16",

}

Download

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 -