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Their energy barriers are typically ca. 11\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>, 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 (<jats:italic>\u03c1<\/jats: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.<\/jats:p>","DOI":"10.1002\/anie.201708649","type":"journal-article","created":{"date-parts":[[2017,11,17]],"date-time":"2017-11-17T19:56:39Z","timestamp":1510948599000},"page":"1480-1484","source":"Crossref","is-referenced-by-count":29,"title":["Dynamic Cross\u2010Exchange in Halophosphonium Species: Direct Observation of Stereochemical Inversion in the Course of an S<sub>N<\/sub>2 Process"],"prefix":"10.1002","volume":"57","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1444-234X","authenticated-orcid":false,"given":"Kirill","family":"Nikitin","sequence":"first","affiliation":[{"name":"School of Chemistry University College Dublin  Belfield Dublin Ireland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Elizabeth 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