Tetragonal phosphorus(v) cations as tunable and robust catalytic Lewis acids
Name
c9sc02463h.pdf
Description
Published version
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740.96 KB
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Adobe PDF
Checksum (MD5)
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Author(s)
Gilhula, James C.
Radosevich, Alexander T.
Date Issued
June 18, 2019
Journal
Chemical Science
Publisher
Royal Society of Chemistry (RSC)
Citation
Gilhula, James C., and Alexander T. Radosevich. "Tetragonal phosphorus(v) cations as tunable and robust catalytic Lewis acids." Chemical Science 10, 30 (2019): 7177-7182 © 2019 The Royal Society of Chemistry
Version
Final published version
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(C[subscript 6]F[subscript 5])[subscript 4]] (Ar = C[subscript 6]H[subscript 5], 3,5-(CF[subscript 3])[subscript 2]C[subscript 6]H[subscript 3]; cor = 5,10,15-(C[subscript 6]H[subscript 5])[subscript 3]corrolato[superscript 3-], 5,10,15-(C[subscript 6]F[subscript 5])[subscript 3]corrolato[superscript 3-]) 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, C[subscript sp3]-H bond functionalization, and carbohydrate deoxygenation reactions.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution 3.0 unported license
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DOI of Published Version
https://doi.org/10.1039/c9sc02463h
