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

被引：11

作者：

Aljuhani, Maha A. ^{[1
]}

Zhang, Ziyun ^{[1
]}

Barman, Samir ^{[1
]}

El Eter, Mohamad ^{[1
]}

Failvene, Laura ^{[1
]}

Ould-Chikh, Samy ^{[1
]}

Guan, Erjia ^{[3
]}

Abou-Hamad, Edy ^{[2
]}

Emwas, Abdul-Hamid ^{[2
]}

Pelletier, Jeremie D. A. ^{[1
]}

Gates, Bruce C. ^{[3
]}

Cavallo, Luigi ^{[1
]}

Basset, Jean-Marie ^{[1
]}

机构：

[1] KAUST, Div Phys Sci & Engn, KAUST Catalysis Ctr, Thuwal 239556900, Saudi Arabia

[2] KAUST, Core Labs, Thuwal 239556900, Saudi Arabia

[3] Univ Calif Davis, Dept Chem Engn, Davis, CA 95616 USA

来源：

ACS CATALYSIS | 2019年 / 9卷 / 09期

关键词：

heterogeneous catalysis; hydroamination; SOMF; azametallacyclobutene; imido fragment; CATALYTIC HYDROAMINATION; METATHESIS;

D O I：

10.1021/acscatal.9b02184

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Selective hydroamination of terminal alkynes with primary aryl amines is catalyzed by an unprecedented well-defined silica-supported tantalum complex [( Si-O-)Ta(eta(1)sigma-NEtMe)(2)(=(NBu)-Bu-t)]. A molecular-level characterization of the surface organometallic Ta species was done with the help of characterization techniques including in situ infrared, H-1 and C-13 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 N-15 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.

引用

页码：8719 / 8725

页数：13