Mechanistic Study of Hydroamination of Alkyne through
Tantalum-Based Silica-Supported Surface Species
Posted on 2019-08-23 - 15:04
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 techniques including in situ infrared, 1H and 13C solid-state NMR (including double and
triple quanta sequencing), 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 intermediate resulting
from the anti-Markovnikov addition of the alkyne to the surface tantalum
imido. A mechanism is proposed that is on the isolation of all intermediates.
A density functional theory (DFT) calculation has confirmed all the
elementary steps and intermediates that were fully characterized.
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Aljuhani, Maha A.; Zhang, Ziyun; Barman, Samir; El Eter, Mohamad; Failvene, Laura; Ould-Chikh, Samy; et al. (2019). Mechanistic Study of Hydroamination of Alkyne through
Tantalum-Based Silica-Supported Surface Species. ACS Publications. Collection. https://doi.org/10.1021/acscatal.9b02184
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AUTHORS (13)
MA
Maha A. Aljuhani
ZZ
Ziyun Zhang
SB
Samir Barman
ME
Mohamad El Eter
LF
Laura Failvene
SO
Samy Ould-Chikh
EG
Erjia Guan
EA
Edy Abou-Hamad
AE
Abdul-Hamid Emwas
JP
Jérémie
D. A. Pelletier
BG
Bruce C. Gates
LC
Luigi Cavallo
JB
Jean-Marie Basset
KEYWORDS
surface organometallic Ta speciesTantalum-Based Silica-Supported Surface Species4- membered metallacycle ringterminal alkynesmolecular-level characterizationanti-Markovnikov additionaryl aminesMechanistic StudyX-ray absorption spectroscopiessilica-supported tantalumcharacterization techniques1 HintermediateDNP-SENS 15 N characterizationDFTNMRsurface tantalum imido13 C