Mechanistic study of hydroamination of alkyne through tantalum-based silica-supported surface species

M.A. Aljuhani, Z. Zhang, S. Barman, M. El Eter, L. Falivene, S. Ould-Chikh, E. Guan, E. Abou-Hamad, A.-H. Emwas, J.D.A. Pelletier, B. C. Gates, L. Cavallo, J.-M. Basset
ACS Catalysis, (2019)

Mechanistic study of hydroamination of alkyne through tantalum-based silica-supported surface species

Keywords

Heterogeneous catalysis, Hydroamination, SOMF, Azametallacyclobutene, Imido fragment

Abstract

​Selective hydroamination of terminal alkynes with primary aryl amines is catalyzed by an unprecedented well-defined silica-supported tantalum complex [(≡Si-O-)Ta(η1σ-NEtMe)2(=NtBu)]. A molecular-level characterization of the surface organometallic Ta species was done with the help of characterization tech-niques including as in situ infrared, in situ elemental microanal-ysis, 1H and 13C solid-state NMR (including double and triple quanta sequence), and X-ray absorption spectroscopies. These were complemented by the state-of-the-art DNP-SENS 15N characterization. Several catalytic intermediates have been isolated in particular the 4-membered metallacycle ring inter-mediate resulting from the anti Markovnikov addition of the alkyne to the surface tantalum imido. The mechanism proposed was based on the isolation of all intermediates. A DFT calcula-tion has confirmed all the elementary steps and intermediates that were fully characterized.

Code

DOI: 10.1021/acscatal.9b02184

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