School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978, Israel.
J Am Chem Soc. 2023 Feb 15;145(6):3786-3794. doi: 10.1021/jacs.2c13318. Epub 2023 Feb 4.
The synthesis, isolation, and reactivity of a cationic, geometrically constrained σ-P compound in the hexaphenyl-carbodiphosphoranyl-based pincer-type ligand () are reported. reacts with electron-poor fluoroarenes via an oxidative addition-type reaction of the C-F bond to the P-center, yielding new fluorophosphorane-type species (P). This reactivity of was used in the catalytic hydrodefluorination of Ar-F bonds with PhSiH, and in a catalytic C-N bond-forming cross-coupling reactions between fluoroarenes and aminosilanes. Importantly, in these catalytic reactions closely mimics the mode of action of the transition metal-based catalysts.
报道了一种基于六苯并膦基的钳式配体的阳离子、几何受限的 σ-P 化合物的合成、分离和反应性。 通过 C-F 键对 P 中心的氧化加成反应与缺电子的氟代芳烃反应，生成新的氟膦烷型物种（P）。 这种 的反应性用于在 PhSiH 存在下催化 Ar-F 键的氢氟消除反应，以及在氟代芳烃和氨基硅烷之间的催化 C-N 键形成交叉偶联反应中。 重要的是， 在这些催化反应中，它紧密模拟了基于过渡金属的催化剂的作用模式。
