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- Title
Dynamic Cross‐Exchange in Halophosphonium Species: Direct Observation of Stereochemical Inversion in the Course of an S<sub>N</sub>2 Process.
- Authors
Nikitin, Kirill; Jennings, Elizabeth V.; Al sulaimi, Sulaiman; Ortin, Yannick; Gilheany, Declan G.
- Abstract
Abstract: The complex fluxional interconversions between otherwise very similar phosphonium bromides and chlorides R3PX+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 (<italic>ρ</italic> 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.
- Subjects
PHOSPHONIUM compounds; BROMIDES; CHLORIDES; NUCLEAR magnetic resonance; NUCLEOPHILIC reactions
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 6, p1496
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201708649