Syntheses of Tungsten Imido Cyclohexylidene Complexes Using Perfluoro‐ t ‐Butanol or Hexafluoro‐ t ‐Butanol as Acids

Maji, Milan; Riedel, René; Schrock, Richard R.; Conley, Matthew P.; Carta, Veronica

doi:10.1002/anie.202410923

Title: Syntheses of Tungsten Imido Cyclohexylidene Complexes Using Perfluoro‐ t ‐Butanol or Hexafluoro‐ t ‐Butanol as Acids

Journal Article · 29 October 2024 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202410923 · OSTI ID:2479815

^[1]; Riedel, René ^[1];

^[1];

^[1]

Department of Chemistry University of California at Riverside Riverside California 92521 USA

Abstract The fluorinated alcohols, (CF ₃ ) ₃ COH (R _F9 OH) and (CF ₃ ) ₂ MeCOH (R _F6 OH), react with W(NR) ₂ Cy ₂ (Cy=Cyclohexyl; R=2,6‐diisopropylphenyl or 1‐adamantyl) in C ₆ D ₆ at 55 °C to give cyclohexylidene complexes. Traditional routes to terminal alkylidene complexes (neopentylidene or neophylidene) have used either triflic acid or HCl (rarely), but relatively weak fluorinated acids are sufficient and active bisalkoxide catalysts are therefore prepared directly. An α hydrogen abstraction reaction to give a cyclohexylidene complex from a biscyclohexyl complex appears to be as facile as α hydrogen abstraction to give a neopentylidene or neophylidene ligand, but isomerization of a cyclohexene formed through β hydrogen abstraction is also a possibility. The OR _F9 ligands can be replaced readily with dimethylpyrrolide (Me ₂ Pyr) or other more basic alkoxides. Single crystal X‐ray studies were carried out on W(NAr) ₂ Cy ₂ , W(NAr)(OR _F9 ) ₂ (C ₆ H ₁₀ )(ArNH ₂ ), W(NAr)(OR _F6 ) ₂ (C ₆ H ₁₀ )(ArNH ₂ ), W(NAd)(OR _F9 ) ₂ (C ₆ H ₁₀ )(AdNH ₂ ), W(NAr)(O‐ i ‐Pr _F6 ) ₃ Cy, and W(NAd)(η ¹ ‐Me ₂ Pyr) ₂ (C ₆ H ₁₀ ) (C ₆ H ₁₀ =cyclohexylidene).

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0023344

OSTI ID:: 2479815

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 49 Vol. 63; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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