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. 2023 Feb 15;145(6):3786-3794.
doi: 10.1021/jacs.2c13318. Epub 2023 Feb 4.

Metallomimetic Chemistry of a Cationic, Geometrically Constrained Phosphine in the Catalytic Hydrodefluorination and Amination of Ar-F Bonds

Karina Chulsky  1 , Irina Malahov  1 , Deependra Bawari  1 , Roman Dobrovetsky  1
Affiliations

Metallomimetic Chemistry of a Cationic, Geometrically Constrained Phosphine in the Catalytic Hydrodefluorination and Amination of Ar-F Bonds

Karina Chulsky et al. J Am Chem Soc. .

Abstract

The synthesis, isolation, and reactivity of a cationic, geometrically constrained σ3-P compound in the hexaphenyl-carbodiphosphoranyl-based pincer-type ligand (1+) are reported. 1+ reacts with electron-poor fluoroarenes via an oxidative addition-type reaction of the C-F bond to the PIII-center, yielding new fluorophosphorane-type species (PV). This reactivity of 1+ was used in the catalytic hydrodefluorination of Ar-F bonds with PhSiH3, and in a catalytic C-N bond-forming cross-coupling reactions between fluoroarenes and aminosilanes. Importantly, 1+ in these catalytic reactions closely mimics the mode of action of the transition metal-based catalysts.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Metallomimetic chemistry of geometrically constrained PIII species. Previously reported stepwise, noncatalytic hydrodefluorination of fluoroarenes (top); this work, catalytic hydrodefluorination and amination of fluoroarenes (bottom).
Figure 2
Figure 2
POV-ray depiction of [1+][PF6]. Thermal ellipsoids at 30% probability; hydrogen atoms were omitted for clarity.
Scheme 1
Scheme 1. Synthesis of [1+][Cl] and [1+][PF6]
Figure 3
Figure 3
QTAIM analysis of 1+.
Scheme 2
Scheme 2. Reaction between [1+][PF6] and Excess of 3 Producing the Product of a Formal Oxidative Addition-type Reaction, [4+][PF6]
The 31P NMR spectrum of [4+][PF6] is shown in the inset.
Scheme 3
Scheme 3. Thermally Induced Reaction of [4+][PF6] Producing [1+-F2][PF6] and 5
Figure 4
Figure 4
POV-ray depiction of [1+-F2][PF6]. Thermal ellipsoids at 30% probability; hydrogen atoms were omitted for clarity.
Scheme 4
Scheme 4. Stoichiometric Reaction between [4+][PF6] and PhSiH3 Producing the Product of Hydrodefluorination 7, [1+][PF6], and PhSiF3 via Intermediate [6+][PF6]
Scheme 5
Scheme 5. Hydrodefluorination and C–N Bond-Forming Cross-Coupling Reactions Catalyzed by 1+
Figure 5
Figure 5
DFT-calculated (BP86-D3/def2TZVP) potential energy surface of the proposed mechanism of 1+-catalyzed hydrodefluorination of 3 by PhSiH3. Free Gibbs energies (enthalpies) are given relative to the starting materials.
See this image and copyright information in PMC

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