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Although qualitative descriptions of the impact of structure and symmetry on \u03c3<jats:sup>3<\/jats:sup>\u2010P complexes have been proposed, electronic structure variations responsible for biphilic reactivity have yet to be elucidated experimentally. Reported here are P K\u2010edge XANES data and complementary TDDFT calculations for a series of structurally modified P(N)<jats:sub>3<\/jats:sub> complexes that both validate and quantify electronic structure variations proposed to give rise to biphilic reactions at phosphorus. These data are presented alongside experimentally referenced electronic structure calculations that reveal nontrigonal structures predicted to further enhance biphilic reactivity in \u03c3<jats:sup>3<\/jats:sup>\u2010P ligands and catalysts.<\/jats:p>","DOI":"10.1002\/anie.201901779","type":"journal-article","created":{"date-parts":[[2019,3,22]],"date-time":"2019-03-22T16:29:36Z","timestamp":1553272176000},"page":"6993-6998","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":68,"title":["Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds"],"prefix":"10.1002","volume":"58","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3836-127X","authenticated-orcid":false,"given":"Kyounghoon","family":"Lee","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of Iowa  Iowa City IA 52242 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anastasia V.","family":"Blake","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Iowa  Iowa City IA 52242 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Akira","family":"Tanushi","sequence":"additional","affiliation":[{"name":"Department of Chemistry Massachusetts Institute of Technology  Cambridge MA 02139 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sean M.","family":"McCarthy","sequence":"additional","affiliation":[{"name":"Department of Chemistry Nalas Engineering Services, Inc.  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