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

Maha A. Aljuhani, Ziyun Zhang, Samir Barman, Mohamad El Eter, Laura Falivene, Samy Ould-Chikh, Erjia Guan, Edy Abou-Hamad, Abdul-Hamid M. Emwas, Jeremie Pelletier, Bruce C. Gates, Luigi Cavallo, Jean-Marie Basset

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

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.
Original languageEnglish (US)
Pages (from-to)8719-8725
Number of pages7
JournalACS Catalysis
Volume9
Issue number9
DOIs
StatePublished - Aug 6 2019

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