Dynamic Cross‐Exchange in Halophosphonium Species: Direct Observation of Stereochemical Inversion in the Course of an SN2 Process. (6th December 2017)

• Record Type: Journal Article
• Authors: Nikitin, Kirill; Jennings, Elizabeth V.; Al Sulaimi, Sulaiman; Ortin, Yannick; Gilheany, Declan G.
• Is Part Of: Angewandte Chemie. Volume 130:Number 6(2018)
• Page Start: 1496
• Page End: 1500
• Publication Date: 2017-12-06
• Subjects: Konfigurationsumkehr -- NMR-Spektroskopie -- Nukleophile Substitutionen -- Phosphor -- Stereochemie; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201708649
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The complex fluxional interconversions between otherwise very similar phosphonium bromides and chlorides R3 PX + X − (R=Alk, Ar, X=Cl or Br) were studied by NMR techniques. Their energy barriers are typically ca. 11 kcal mol −1, but rise rapidly as bulky groups are attached to phosphorus, revealing the importance of steric factors. In contrast, electronic effects, as measured by Hammett analysis, are modest ( ρ 1.46) but still clearly indicate negative charge flow towards phosphorus in the transition state. Most significantly, detailed analysis of the exchange pathways unequivocally, and for the first time in any such process, shows that nucleophilic attack of the nucleophilic anion on the tetrahedral centre results in inversion of configuration.