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Treatment of<jats:bold>1a<\/jats:bold>\u22c5Fp<jats:sup>+<\/jats:sup>with [(Me<jats:sub>2<\/jats:sub>N)<jats:sub>3<\/jats:sub>S][Me<jats:sub>3<\/jats:sub>SiF<jats:sub>2<\/jats:sub>] results in fluoride addition to the<jats:italic>P<\/jats:italic>\u2010center, giving the isolable crystalline fluorometallophosphorane<jats:bold>1a<jats:sup>F<\/jats:sup><\/jats:bold>\u22c5Fp that allows a crystallographic assessment of the variance in the Fe\u2212P bond as a function of P\u2010coordination number. The nonspectator reactivity of<jats:bold>1a<\/jats:bold>\u22c5Fp<jats:sup>+<\/jats:sup>is rationalized on the basis of electronic structure arguments and by comparison to trigonal analogue (Me<jats:sub>2<\/jats:sub>N)<jats:sub>3<\/jats:sub>P\u22c5Fp<jats:sup>+<\/jats:sup>(i.e.<jats:bold>1b<\/jats:bold>\u22c5Fp<jats:sup>+<\/jats:sup>), which is inert to fluoride addition. These observations establish a nonspectator L\/X\u2010switching in (\u03c3<jats:sup>3<\/jats:sup>\u2010P)\u2013M complexes by reversible access to higher\u2010coordinate phosphorus ligand fragments.<\/jats:p>","DOI":"10.1002\/anie.201909686","type":"journal-article","created":{"date-parts":[[2019,8,30]],"date-time":"2019-08-30T14:50:28Z","timestamp":1567176628000},"page":"15005-15009","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":24,"title":["A Nontrigonal Tricoordinate Phosphorus Ligand Exhibiting Reversible \u201cNonspectator\u201d L\/X\u2010Switching"],"prefix":"10.1002","volume":"58","author":[{"given":"Gregory T.","family":"Cleveland","sequence":"first","affiliation":[{"name":"Department of Chemistry Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 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