Mechanistic Study of Hydroamination of Alkyne through Tantalum-Based Silica-Supported Surface Species

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

doi:10.1021/acscatal.9b02184

Mechanistic Study of Hydroamination of Alkyne through Tantalum-Based Silica-Supported Surface Species

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

14 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(Î•¹σ-NEtMe)₂(=N^tBu)]. 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.

Original language	English
Pages (from-to)	8719-8725
Number of pages	7
Journal	ACS Catalysis
Volume	9
Issue number	9
DOIs	https://doi.org/10.1021/acscatal.9b02184
State	Published - 6 Sep 2019
Externally published	Yes

Bibliographical note

Funding Information:
The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge Andrei Gurinov for his assistance with the NMR measurements. The work at the University of California was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (DE-FG02-04ER15513). We acknowledge the European Synchrotron Radiation Facility for the provision of the synchrotron radiation facilities and thank Antonio Aguilar for the assistance with using beamline BM30 B.

Publisher Copyright:
© 2019 American Chemical Society.

Keywords

SOMF
azametallacyclobutene
heterogeneous catalysis
hydroamination
imido fragment

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1021/acscatal.9b02184

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Aljuhani, M. A., Zhang, Z., Barman, S., El Eter, M., Failvene, L., Ould-Chikh, S., Guan, E., Abou-Hamad, E., Emwas, A. H., Pelletier, J. D. A., Gates, B. C., Cavallo, L., & Basset, J. M. (2019). Mechanistic Study of Hydroamination of Alkyne through Tantalum-Based Silica-Supported Surface Species. ACS Catalysis, 9(9), 8719-8725. https://doi.org/10.1021/acscatal.9b02184

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title = "Mechanistic Study of Hydroamination of Alkyne through Tantalum-Based Silica-Supported Surface Species",

abstract = "Selective hydroamination of terminal alkynes with primary aryl amines is catalyzed by an unprecedented well-defined silica-supported tantalum complex [(Si-O-)Ta({\^I}•1σ-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.",

keywords = "SOMF, azametallacyclobutene, heterogeneous catalysis, hydroamination, imido fragment",

author = "Aljuhani, \{Maha A.\} and Ziyun Zhang and Samir Barman and \{El Eter\}, Mohamad and Laura Failvene and Samy Ould-Chikh and Erjia Guan and Edy Abou-Hamad and Emwas, \{Abdul Hamid\} and Pelletier, \{J{\'e}r{\'e}mie D.A.\} and Gates, \{Bruce C.\} and Luigi Cavallo and Basset, \{Jean Marie\}",

note = "Funding Information: The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge Andrei Gurinov for his assistance with the NMR measurements. The work at the University of California was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (DE-FG02-04ER15513). We acknowledge the European Synchrotron Radiation Facility for the provision of the synchrotron radiation facilities and thank Antonio Aguilar for the assistance with using beamline BM30 B. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = sep,

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doi = "10.1021/acscatal.9b02184",

language = "English",

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pages = "8719--8725",

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AU - Aljuhani, Maha A.

AU - Zhang, Ziyun

AU - Barman, Samir

AU - El Eter, Mohamad

AU - Failvene, Laura

AU - Ould-Chikh, Samy

AU - Guan, Erjia

AU - Abou-Hamad, Edy

AU - Emwas, Abdul Hamid

AU - Pelletier, Jérémie D.A.

AU - Gates, Bruce C.

AU - Cavallo, Luigi

AU - Basset, Jean Marie

N1 - Funding Information: The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge Andrei Gurinov for his assistance with the NMR measurements. The work at the University of California was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (DE-FG02-04ER15513). We acknowledge the European Synchrotron Radiation Facility for the provision of the synchrotron radiation facilities and thank Antonio Aguilar for the assistance with using beamline BM30 B. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/9/6

Y1 - 2019/9/6

N2 - Selective hydroamination of terminal alkynes with primary aryl amines is catalyzed by an unprecedented well-defined silica-supported tantalum complex [(Si-O-)Ta(Î•1σ-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.

AB - Selective hydroamination of terminal alkynes with primary aryl amines is catalyzed by an unprecedented well-defined silica-supported tantalum complex [(Si-O-)Ta(Î•1σ-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.

KW - SOMF

KW - azametallacyclobutene

KW - heterogeneous catalysis

KW - hydroamination

KW - imido fragment

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DO - 10.1021/acscatal.9b02184

M3 - Article

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SN - 2155-5435

VL - 9

SP - 8719

EP - 8725

JO - ACS Catalysis

JF - ACS Catalysis

IS - 9

ER -

Mechanistic Study of Hydroamination of Alkyne through Tantalum-Based Silica-Supported Surface Species

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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