TY - JOUR
T1 - Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application
AU - Hamzaoui, Bilel
AU - Pelletier, Jeremie
AU - Abou-Hamad, Edy
AU - Chen, Yin
AU - El Eter, Mohamad
AU - Chermak, Edrisse
AU - Cavallo, Luigi
AU - Basset, Jean-Marie
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The authors wish to thank King Abdullah University of Science and Technology for continuous support.
PY - 2016/1/27
Y1 - 2016/1/27
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/621685
UR - http://onlinelibrary.wiley.com/doi/10.1002/chem.201504439/full
UR - http://www.scopus.com/inward/record.url?scp=84960945737&partnerID=8YFLogxK
U2 - 10.1002/chem.201504439
DO - 10.1002/chem.201504439
M3 - Article
C2 - 26875939
SN - 0947-6539
VL - 22
SP - 3000
EP - 3008
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 9
ER -