Solid‐State NMR and DFT Studies on the Formation of Well‐Defined Silica‐Supported Tantallaaziridines: From Synthesis to Catalytic Application |
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| Authors: | Bilel Hamzaoui Dr Jérémie D A Pelletier Dr Edy Abou‐Hamad Dr Yin Chen Dr Mohamed El?Eter Dr Edrisse Chermak Prof Luigi Cavallo Prof Jean‐Marie Basset |
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| Affiliation: | King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia |
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| 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. |
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| Keywords: | hydroamination metallacycles solid-state NMR spectroscopy supported catalysts tantalum |
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