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dc.contributor.authorGilhula, James C.
dc.contributor.authorRadosevich, Alexander T.
dc.date.accessioned2020-01-23T16:06:37Z
dc.date.available2020-01-23T16:06:37Z
dc.date.issued2019-06-18
dc.date.submitted2019-05-20
dc.identifier.issn2041-6520
dc.identifier.issn2041-6539
dc.identifier.urihttps://hdl.handle.net/1721.1/123554
dc.description.abstractThe 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.en_US
dc.language.isoen
dc.publisherRoyal Society of Chemistry (RSC)en_US
dc.relation.isversionofhttp://dx.doi.org/10.1039/c9sc02463hen_US
dc.rightsCreative Commons Attribution 3.0 unported licenseen_US
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/en_US
dc.sourceRoyal Society of Chemistry (RSC)en_US
dc.titleTetragonal phosphorus(v) cations as tunable and robust catalytic Lewis acidsen_US
dc.typeArticleen_US
dc.identifier.citationGilhula, 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 Chemistryen_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistryen_US
dc.relation.journalChemical Scienceen_US
dc.eprint.versionFinal published versionen_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/PeerRevieweden_US
dc.date.updated2020-01-06T18:10:24Z
dspace.date.submission2020-01-06T18:10:27Z
mit.journal.volume10en_US
mit.journal.issue30en_US


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