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

B. Hamzoui, J. Pelletier, E. A-Hamad, Y. Chen, M. El-Eter, E. Chermak, L. Cavallo, J-. Basset
Volume 22, Issue 9, 3000-3008, (2016)

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

Keywords

N-alkyl aryl amine

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.

Code

DOI: 10.1002/chem.201504439

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