Titanium‐Catalyzed Defluorination of Poly(Vinyl Fluoride) and Poly(Vinylidene Fluoride) Under Friedel–Crafts Conditions
Abstract
The defluorination of poly(vinyl fluoride) (PVF) and poly(vinylidene fluoride) (PVDF) fluoropolymers catalyzed by titanium species in the presence of triethylsilane (Et 3 SiH) and aromatic solvents is reported. Commercially available Ti complexes (e.g., [Cp 2 TiCl 2 ] ( Ti3 ) or [CpTiCl 3 ] ( Ti5 ); Cp = η 5 ‐C 5 H 5 ) activated by the silylium reagent [(Et 3 Si) 2 H](B(C 6 F 5 ) 4 ) ( Si + ) defluorinate PVF and PVDF with turnover frequencies (TOF) of up to 3.7 h −1 , affording copolymers with low residual fluorine content (down to 0.8%). The obtained polymers were characterized by multiple techniques including solid‐state nuclear magnetic resonance (NMR) and Fourier‐transform Infrared (FTIR) spectroscopies, combustion ion chromatography (CIC), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). Density functional theory (DFT) calculations conducted in bromobenzene on 2‐fluoropropane as a model indicate that the turnover‐limiting step is the concerted fluoride abstraction (by Ti)/hydride transfer (by Et 3 SiH).
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BibTeX
@article{moigne2026titaniumcatalyzed,
title = {{Titanium‐Catalyzed Defluorination of Poly(Vinyl Fluoride) and Poly(Vinylidene Fluoride) Under Friedel–Crafts Conditions}},
author = {Louis Le Moigne and Marie Sircoglou and Quentin Bonnin and Marie‐josé Penouilh and Joan Vignolle and Etienne Grau and Cédric Le Coz and Mélanie Bousquet and Paul Fleurat‐lessard and Adrien T Normand},
journal = {Angewandte Chemie International Edition},
year = {2026},
month = aug,
doi = {10.1002/anie.4183926},
url = {https://hal.science/hal-05740055v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Titanium‐Catalyzed Defluorination of Poly(Vinyl Fluoride) and Poly(Vinylidene Fluoride) Under Friedel–Crafts Conditions
AU - Louis Le Moigne
AU - Marie Sircoglou
AU - Quentin Bonnin
AU - Marie‐josé Penouilh
AU - Joan Vignolle
AU - Etienne Grau
AU - Cédric Le Coz
AU - Mélanie Bousquet
AU - Paul Fleurat‐lessard
AU - Adrien T Normand
PY - 2026
DA - 2026/08/23
JO - Angewandte Chemie International Edition
DO - 10.1002/anie.4183926
UR - https://hal.science/hal-05740055v1
AB - The defluorination of poly(vinyl fluoride) (PVF) and poly(vinylidene fluoride) (PVDF) fluoropolymers catalyzed by titanium species in the presence of triethylsilane (Et 3 SiH) and aromatic solvents is reported. Commercially available Ti complexes (e.g., [Cp 2 TiCl 2 ] ( Ti3 ) or [CpTiCl 3 ] ( Ti5 ); Cp = η 5 ‐C 5 H 5 ) activated by the silylium reagent [(Et 3 Si) 2 H](B(C 6 F 5 ) 4 ) ( Si + ) defluorinate PVF and PVDF with turnover frequencies (TOF) of up to 3.7 h −1 , affording copolymers with low residual fluorine content (down to 0.8%). The obtained polymers were characterized by multiple techniques including solid‐state nuclear magnetic resonance (NMR) and Fourier‐transform Infrared (FTIR) spectroscopies, combustion ion chromatography (CIC), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). Density functional theory (DFT) calculations conducted in bromobenzene on 2‐fluoropropane as a model indicate that the turnover‐limiting step is the concerted fluoride abstraction (by Ti)/hydride transfer (by Et 3 SiH).
SN - 1433-7851
SN - 1521-3773
ER -