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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.; ... Show more Show less
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Abstract
Constraining σ3-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 σ3-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 σ3-P ligands and catalysts.
Date issued
2019-05
URI
https://hdl.handle.net/1721.1/129698
Department
Massachusetts Institute of Technology. Department of Chemistry
Journal
Angewandte Chemie - International Edition
Publisher
Wiley
Citation
Lee, Kyounghoon et al. "Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds." Angewandte Chemie - International Edition 58, 21 (May 2019): 6993-6998 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Version: Author's final manuscript
ISSN
1433-7851
1521-3773

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