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

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 P^III-center, yielding new fluorophosphorane-type species (P^V). 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.

SUBMITTER: Chulsky K

PROVIDER: S-EPMC9936586 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

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

Chulsky Karina K Malahov Irina I Bawari Deependra D Dobrovetsky Roman R

Journal of the American Chemical Society 20230204 6

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 catalyti ...[more]

PMID: 36738474

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