Journal article
Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds
Angewandte Chemie (International ed.), Vol.58(21), pp.6993-6998
05/20/2019
DOI: 10.1002/anie.201901779
PMCID: PMC6513703
PMID: 30901511
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.
Double agent: P K‐edge XANES and TDDFT calculations were used to quantify how nontrigonal structural deformations affect the electronic structure and reactivity of a series of P(NNN) compounds. The results suggest that biphilic PIII reactivity reported previously with and without a transition‐metal host stems from a common low‐lying phosphorus‐based acceptor orbital that becomes energetically accessible in response to nontrigonal PIII distortions.
Details
- Title: Subtitle
- Validating the Biphilic Hypothesis of Nontrigonal Phosphorus(III) Compounds
- Creators
- Kyounghoon Lee - The University of IowaAnastasia V Blake - The University of IowaAkira Tanushi - Massachusetts Institute of TechnologySean M McCarthy - Nalas Engineering Services, IncDaniel Kim - Colgate UniversitySydney M Loria - Colgate UniversityCourtney M Donahue - The University of IowaKyle D Spielvogel - The University of IowaJason M Keith - Colgate UniversityScott R Daly - The University of IowaAlexander T Radosevich - Massachusetts Institute of Technology
- Resource Type
- Journal article
- Publication Details
- Angewandte Chemie (International ed.), Vol.58(21), pp.6993-6998
- DOI
- 10.1002/anie.201901779
- PMID
- 30901511
- PMCID
- PMC6513703
- ISSN
- 1433-7851
- eISSN
- 1521-3773
- Number of pages
- 6
- Grant note
- National Science Foundation () (CHE-1724505) National Institute of General Medical Sciences (GM114547) American Chemical Society Petroleum Research Fund (55989-DNI3)
- Language
- English
- Date published
- 05/20/2019
- Academic Unit
- Chemistry
- Record Identifier
- 9984216705802771
Metrics
8 Record Views