Sb‐to‐P Metathesis: A Direct Route to Structurally Constrained, Cationic P<sup>III</sup> Compound
Structurally constrained, cationic P<sup>III</sup> compound [LP][SbCl<sub>4</sub>] with an OCO pincer-type ligand (L) having a central carbene donor was directly synthesized via an Sb-to-P metathesis reaction between PCl<sub>3</sub> and LSb-Cl. [LP][SbCl<sub>4</sub>] was isolated and its reactivity with small molecules (ROH and RNH<sub>2</sub>) was studied, showing that [SbCl<sub>4</sub>]<sup>-</sup> is not an innocent counter anion, but an active participant in these reactions. When the [SbCl<sub>4</sub>]<sup>-</sup> was replaced with the [CB<sub>11</sub>H<sub>12</sub>]<sup>-</sup> ([Cb]<sup>-</sup>) anion, the reactions were redirected to [LP]<sup>+</sup> cation only. The reactions with alcohols and amines led to the equilibrium between the products of the formal E-H (E=O, N) bond oxidative addition to the P-center and products of the P-center/ligand-assisted bond activation. Remarkably, [LP]<sup>+</sup> activated the PhO-H and PhN(H)-H bonds in a reversible, thermoneutral fashion.
Authors
- Irina Malahov
- Roman Dobrovetsky (ORCID: https://orcid.org/0000-0002-6036-4709)
- Deependra Bawari (ORCID: https://orcid.org/0000-0002-5626-2435)
Institutions
- Tel Aviv University (IL)
- Shenkar College of Engineering and Design (IL)
- Exact Sciences (United States) (US)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2024-11-21
- DOI
- https://doi.org/10.1002/anie.202419772
- Citations
- 7
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 1.11