Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds
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,...
| Main Authors: | , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Wiley
2021
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| Online Access: | https://hdl.handle.net/1721.1/129698 |
| _version_ | 1826213903323889664 |
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| author | 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. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry 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. |
| author_sort | Lee, Kyounghoon |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T15:56:40Z |
| format | Article |
| id | mit-1721.1/129698 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T15:56:40Z |
| publishDate | 2021 |
| publisher | Wiley |
| record_format | dspace |
| spelling | mit-1721.1/1296982022-09-29T17:13:44Z Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds 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. Massachusetts Institute of Technology. Department of Chemistry 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. NIH NIGMS (Grant GM114547) NSF (Grant CHE-1724505) 2021-02-05T22:18:13Z 2021-02-05T22:18:13Z 2019-05 2019-03 2020-09-18T15:08:37Z Article http://purl.org/eprint/type/JournalArticle 1433-7851 1521-3773 https://hdl.handle.net/1721.1/129698 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 en http://dx.doi.org/10.1002/anie.201901779 Angewandte Chemie - International Edition Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Wiley PMC |
| spellingShingle | 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. Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds |
| title | Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds |
| title_full | Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds |
| title_fullStr | Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds |
| title_full_unstemmed | Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds |
| title_short | Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds |
| title_sort | validating the biphilic hypothesis of nontrigonal phosphorus iii compounds |
| url | https://hdl.handle.net/1721.1/129698 |
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