| Title: |
Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds |
| Authors: |
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. |
| Contributors: |
National Institute of General Medical Sciences; American Chemical Society Petroleum Research Fund |
| Source: |
Angewandte Chemie International Edition ; volume 58, issue 21, page 6993-6998 ; ISSN 1433-7851 1521-3773 |
| Publisher Information: |
Wiley |
| Publication Year: |
2019 |
| Collection: |
Wiley Online Library (Open Access Articles via Crossref) |
| Description: |
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. |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| DOI: |
10.1002/anie.201901779 |
| Availability: |
https://doi.org/10.1002/anie.201901779; https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201901779; https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201901779; https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.201901779 |
| Rights: |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
| Accession Number: |
edsbas.B4F0F2F6 |
| Database: |
BASE |