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Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds
Author(s) -
Lee Kyounghoon,
Blake Anastasia V.,
Tanushi Akira,
McCarthy Sean M.,
Kim Daniel,
Loria Sydney M.,
Donahue Courtney M.,
Spielvogel Kyle D.,
Keith Jason M.,
Daly Scott R.,
Radosevich Alexander T.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201901779
Subject(s) - reactivity (psychology) , electronic structure , xanes , chemistry , computational chemistry , time dependent density functional theory , phosphorus , transition metal , density functional theory , catalysis , spectroscopy , organic chemistry , physics , medicine , alternative medicine , pathology , quantum mechanics
Constraining σ 3 ‐P compounds in nontrigonal, entatic geometries has proven to be an effective strategy for promoting biphilic oxidative addition reactions more typical of transition metals. Although qualitative descriptions of the impact of structure and symmetry on σ 3 ‐P complexes have been proposed, electronic structure variations responsible for biphilic reactivity have yet to be elucidated experimentally. Reported here are P K‐edge XANES data and complementary TDDFT calculations for a series of structurally modified P(N) 3 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 σ 3 ‐P ligands and catalysts.