Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application

Handle URI:
http://hdl.handle.net/10754/621685
Title:
Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application
Authors:
Hamzaoui, Bilel; Pelletier, Jeremie ( 0000-0002-4709-4898 ) ; Abou-Hamad, Edy; Chen, Yin; El Eter, Mohamad; Chermak, Edrisse ( 0000-0002-2716-5724 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
Single-site, well-defined, silica-supported tantallaaziridine intermediates [≡Si-O-Ta(η2-NRCH2)(NMe2)2] [R=Me (2), Ph (3)] were prepared from silica-supported tetrakis(dimethylamido)tantalum [≡Si-O-Ta(NMe2)4] (1) and fully characterized by FTIR spectroscopy, elemental analysis, and 1H,13C HETCOR and DQ TQ solid-state (SS) NMR spectroscopy. The formation mechanism, by β-H abstraction, was investigated by SS NMR spectroscopy and supported by DFT calculations. The C-H activation of the dimethylamide ligand is favored for R=Ph. The results from catalytic testing in the hydroaminoalkylation of alkenes were consistent with the N-alkyl aryl amine substrates being more efficient than N-dialkyl amines. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Hamzaoui B, Pelletier JDA, Abou-Hamad E, Chen Y, El Eter M, et al. (2016) Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application. Chem Eur J 22: 3000–3008. Available: http://dx.doi.org/10.1002/chem.201504439.
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
27-Jan-2016
DOI:
10.1002/chem.201504439
Type:
Article
ISSN:
0947-6539
Sponsors:
The authors wish to thank King Abdullah University of Science and Technology for continuous support.
Additional Links:
http://onlinelibrary.wiley.com/doi/10.1002/chem.201504439/full
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorHamzaoui, Bilelen
dc.contributor.authorPelletier, Jeremieen
dc.contributor.authorAbou-Hamad, Edyen
dc.contributor.authorChen, Yinen
dc.contributor.authorEl Eter, Mohamaden
dc.contributor.authorChermak, Edrisseen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2016-11-03T13:22:44Z-
dc.date.available2016-11-03T13:22:44Z-
dc.date.issued2016-01-27en
dc.identifier.citationHamzaoui B, Pelletier JDA, Abou-Hamad E, Chen Y, El Eter M, et al. (2016) Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application. Chem Eur J 22: 3000–3008. Available: http://dx.doi.org/10.1002/chem.201504439.en
dc.identifier.issn0947-6539en
dc.identifier.doi10.1002/chem.201504439en
dc.identifier.urihttp://hdl.handle.net/10754/621685-
dc.description.abstractSingle-site, well-defined, silica-supported tantallaaziridine intermediates [≡Si-O-Ta(η2-NRCH2)(NMe2)2] [R=Me (2), Ph (3)] were prepared from silica-supported tetrakis(dimethylamido)tantalum [≡Si-O-Ta(NMe2)4] (1) and fully characterized by FTIR spectroscopy, elemental analysis, and 1H,13C HETCOR and DQ TQ solid-state (SS) NMR spectroscopy. The formation mechanism, by β-H abstraction, was investigated by SS NMR spectroscopy and supported by DFT calculations. The C-H activation of the dimethylamide ligand is favored for R=Ph. The results from catalytic testing in the hydroaminoalkylation of alkenes were consistent with the N-alkyl aryl amine substrates being more efficient than N-dialkyl amines. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en
dc.description.sponsorshipThe authors wish to thank King Abdullah University of Science and Technology for continuous support.en
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/chem.201504439/fullen
dc.subjectHydroaminationen
dc.subjectMetallacyclesen
dc.subjectSolid-state NMR spectroscopyen
dc.subjectSupported catalystsen
dc.subjectTantalumen
dc.titleSolid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Applicationen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalChemistry - A European Journalen
kaust.authorHamzaoui, Bilelen
kaust.authorPelletier, Jeremieen
kaust.authorAbou-Hamad, Edyen
kaust.authorChen, Yinen
kaust.authorEl Eter, Mohamaden
kaust.authorChermak, Edrisseen
kaust.authorCavallo, Luigien
kaust.authorBasset, Jean-Marieen
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