title: Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application.
abstract: Single-site, well-defined, silica-supported tantallaaziridine intermediates [≡Si-O-Ta(η(2) -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 (1) H,(13) C 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.
authors.affiliation: King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Bilel
authors.initials: B
authors.lastname: Hamzaoui
authors.affiliation: King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Jérémie D A
authors.initials: JD
authors.lastname: Pelletier
authors.affiliation: King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Edy
authors.initials: E
authors.lastname: Abou-Hamad
authors.affiliation: King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Yin
authors.initials: Y
authors.lastname: Chen
authors.affiliation: King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Mohamed
authors.initials: M
authors.lastname: El Eter
authors.affiliation: King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Edrisse
authors.initials: E
authors.lastname: Chermak
authors.affiliation: King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Luigi
authors.initials: L
authors.lastname: Cavallo
authors.affiliation: King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia. jeanmarie.basset@kaust.edu.sa.
authors.forename: Jean-Marie
authors.initials: JM
authors.lastname: Basset
keywords: hydroamination; metallacycles; solid-state NMR spectroscopy; supported catalysts; tantalum