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Peer-reviewedCC BY 4.0ChemistryOpen

Reactivity of Rh(I) Complexes Toward Fluorinated Ethers: Activation of Inhalation Anesthetics

  1. 1Department of Chemistry Humboldt‐Universität zu Berlin Berlin Germany

Abstract

The reactivity of [Rh(H)(PEt ₃ ) ₃ ] ( 1 ) toward α‐fluorinated ethers that are commonly used as inhalational anesthetics was studied. Unprecedented reactivity pathways include hydrodehalogenation of sp ³ C─F and C─Cl bonds under mild conditions. The reaction of 1 with sevoflurane (CF ₃ ) ₂ CHOCH ₂ F provides an efficient route to obtain [Rh(F)(PEt ₃ ) ₃ ] ( 2 ) by C( sp ³ )─F bond activation. Furthermore, the phosphine ligand takes part in this reaction, and an F/Et exchange at [Rh(H)(F) ₂ (PEt ₃ ) ₃ ] results in the formation of the fluorophosphine complex trans ‐[Rh(F)(Et ₂ PF)(PEt ₃ ) ₂ ] ( 5 ) upon the release of ethane. On the other hand, an oxidative addition of enflurane CClFHCF ₂ OCF ₂ H at 1 yielded [Rh(H)(Cl)(CFHCF ₂ OCF ₂ H)(PEt ₃ ) ₃ ] ( 8 ), which is followed by a reductive elimination step to yield [Rh(Cl)(PEt ₃ ) ₃ ] ( 7 ) and the hydrofluoroether CFH ₂ CF ₂ OCF ₂ H. When an isomer of enflurane, isoflurane CF ₃ CClHOCF ₂ H, was treated with 1 , complex 7 and CF ₃ CH ₂ OCF ₂ H are generated by C( sp ³ )─Cl bond activation. Additionally, an in situ nucleophilic attack of triethylphosphine at the hydrofluoroether CF ₃ CH ₂ OCF ₂ H gave a unique fluorinated phosphonium salt [CF ₃ CH ₂ PEt ₃ ] ₂ [SiF ₆ ] ( 9 ). Catalytic hydrodechlorination of isoflurane at a mild condition was achieved in the presence of silane HSiPh ₃ using 1 as a catalyst.

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BibTeX
@article{mollasalehi2026reactivity,
  title = {{Reactivity of Rh(I) Complexes Toward Fluorinated Ethers: Activation of Inhalation Anesthetics}},
  author = {Soodeh Mollasalehi and Jakob Bölle and Thomas Braun},
  journal = {ChemistryOpen},
  year = {2026},
  month = nov,
  doi = {10.1002/open.70328},
  url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/open.70328},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Reactivity of Rh(I) Complexes Toward Fluorinated Ethers: Activation of Inhalation Anesthetics
AU  - Soodeh Mollasalehi
AU  - Jakob Bölle
AU  - Thomas Braun
PY  - 2026
DA  - 2026/11/01
JO  - ChemistryOpen
DO  - 10.1002/open.70328
UR  - https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/open.70328
AB  - The reactivity of [Rh(H)(PEt ₃ ) ₃ ] ( 1 ) toward α‐fluorinated ethers that are commonly used as inhalational anesthetics was studied. Unprecedented reactivity pathways include hydrodehalogenation of sp ³ C─F and C─Cl bonds under mild conditions. The reaction of 1 with sevoflurane (CF ₃ ) ₂ CHOCH ₂ F provides an efficient route to obtain [Rh(F)(PEt ₃ ) ₃ ] ( 2 ) by C( sp ³ )─F bond activation. Furthermore, the phosphine ligand takes part in this reaction, and an F/Et exchange at [Rh(H)(F) ₂ (PEt ₃ ) ₃ ] results in the formation of the fluorophosphine complex trans ‐[Rh(F)(Et ₂ PF)(PEt ₃ ) ₂ ] ( 5 ) upon the release of ethane. On the other hand, an oxidative addition of enflurane CClFHCF ₂ OCF ₂ H at 1 yielded [Rh(H)(Cl)(CFHCF ₂ OCF ₂ H)(PEt ₃ ) ₃ ] ( 8 ), which is followed by a reductive elimination step to yield [Rh(Cl)(PEt ₃ ) ₃ ] ( 7 ) and the hydrofluoroether CFH ₂ CF ₂ OCF ₂ H. When an isomer of enflurane, isoflurane CF ₃ CClHOCF ₂ H, was treated with 1 , complex 7 and CF ₃ CH ₂ OCF ₂ H are generated by C( sp ³ )─Cl bond activation. Additionally, an in situ nucleophilic attack of triethylphosphine at the hydrofluoroether CF ₃ CH ₂ OCF ₂ H gave a unique fluorinated phosphonium salt [CF ₃ CH ₂ PEt ₃ ] ₂ [SiF ₆ ] ( 9 ). Catalytic hydrodechlorination of isoflurane at a mild condition was achieved in the presence of silane HSiPh ₃ using 1 as a catalyst.
SN  - 2191-1363
SN  - 2191-1363
ER  -