Tetragonal phosphorus( v ) cations as tunable and robust catalytic Lewis acids
Abstract
The synthesis and catalytic reactivity of a class of water-tolerant cationic phosphorus-based Lewis acids is reported. Corrole-based phosphorus(V) cations of the type [ArP(cor)][B(C6F5)4] (Ar = C6H5, 3,5-(CF3)2C6H3; cor = 5,10,15-(C6H5)3corrolato3–, 5,10,15-(C6F5)3corrolato3–) were synthesized and characterized by NMR and X-ray diffraction. The visible electronic absorption spectra of these cationic phosphacorroles depend strongly on the coordination environment at phosphorus, and their Lewis acidities are quantified by spectrophotometric titrations. DFT analyses establish that the character of the P-acceptor orbital comprises P–N antibonding interactions in the basal plane of the phosphacorrole. Consequently, the cationic phosphacorroles display unprecedented stability to water and alcohols while remaining highly active and robust Lewis acid catalysts for carbonyl hydrosilylation, Csp3–H bond functionalization, and carbohydrate deoxygenation reactions.
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF)
- OSTI Identifier:
- 1529036
- Alternate Identifier(s):
- OSTI ID: 1561309
- Grant/Contract Number:
- AC02-06CH11357; CHE-1724505; CHE-1900060; NSF/CHE-1346572; NSF/DMR-1531283
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 30; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Gilhula, James C., and Radosevich, Alexander T.. Tetragonal phosphorus( v ) cations as tunable and robust catalytic Lewis acids. United Kingdom: N. p., 2019.
Web. doi:10.1039/C9SC02463H.
Gilhula, James C., & Radosevich, Alexander T.. Tetragonal phosphorus( v ) cations as tunable and robust catalytic Lewis acids. United Kingdom. https://doi.org/10.1039/C9SC02463H
Gilhula, James C., and Radosevich, Alexander T.. Wed .
"Tetragonal phosphorus( v ) cations as tunable and robust catalytic Lewis acids". United Kingdom. https://doi.org/10.1039/C9SC02463H.
@article{osti_1529036,
title = {Tetragonal phosphorus( v ) cations as tunable and robust catalytic Lewis acids},
author = {Gilhula, James C. and Radosevich, Alexander T.},
abstractNote = {The synthesis and catalytic reactivity of a class of water-tolerant cationic phosphorus-based Lewis acids is reported. Corrole-based phosphorus(V) cations of the type [ArP(cor)][B(C6F5)4] (Ar = C6H5, 3,5-(CF3)2C6H3; cor = 5,10,15-(C6H5)3corrolato3–, 5,10,15-(C6F5)3corrolato3–) were synthesized and characterized by NMR and X-ray diffraction. The visible electronic absorption spectra of these cationic phosphacorroles depend strongly on the coordination environment at phosphorus, and their Lewis acidities are quantified by spectrophotometric titrations. DFT analyses establish that the character of the P-acceptor orbital comprises P–N antibonding interactions in the basal plane of the phosphacorrole. Consequently, the cationic phosphacorroles display unprecedented stability to water and alcohols while remaining highly active and robust Lewis acid catalysts for carbonyl hydrosilylation, Csp3–H bond functionalization, and carbohydrate deoxygenation reactions.},
doi = {10.1039/C9SC02463H},
journal = {Chemical Science},
number = 30,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {7}
}
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