Hydroamination of Phenylacetylene with Aniline over Gold Nanoparticles Embedded in the Boron Imidazolate Framework BIF-66 and Zeolitic Imidazolate Framework ZIF-67

Vera I Isaeva; Konstantinos Papathanasiou; Vladimir V Chernyshev; Lev Glukhov; Grigory Deyko; Kamal Kumar Bisht; Olga P Tkachenko; Serguei V Savilov; Nikolai A Davshan; Leonid M Kustov

doi:10.1021/acsami.1c14359

Hydroamination of Phenylacetylene with Aniline over Gold Nanoparticles Embedded in the Boron Imidazolate Framework BIF-66 and Zeolitic Imidazolate Framework ZIF-67

ACS Appl Mater Interfaces. 2021 Dec 22;13(50):59803-59819. doi: 10.1021/acsami.1c14359. Epub 2021 Dec 14.

Authors

Affiliations

¹ N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospect 47, Moscow 119991, Russia.
² National University of Science and Technology MISiS, Leninsky prospect 4, Moscow 119991, Russia.
³ Chemistry Department, Moscow State University, Leninskie Gory 1, bldg. 3, Moscow 119992, Russia.
⁴ A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, 31 Leninsky prospect, Moscow 119071, Russian Federation.
⁵ Department of Chemistry, RGU Government Post Graduate College Uttarkashi, Uttarkashi, 2491936 Uttarakhand, India.

PMID: 34904440
DOI: 10.1021/acsami.1c14359

Abstract

The hydroamination of alkynes is an atom-economy process in the organic synthesis for the C-N bond formation, thereby allowing the production of fine chemicals and intermediates. However, direct interaction between alkynes and amines is complicated due to the electron enrichment of both compounds. Therefore, efficient hydroamination catalysts, especially heterogeneous ones, are in great demand. This work aimed at the development of novel heterogeneous catalysts based on zeolite-like metal-organic frameworks for phenylacetylene hydroamination. The sodalite (SOD) type zeolitic imidazolate framework ZIF-67 (Co(meim)₂, meim = 2-methylimidazolate) and boron imidazolate framework BIF-66 ({Co[B(im)₄]₂}_n, im = imidazolate) were studied as the carriers for the gold nanoparticles (Au-NPs). Au-NPs were embedded in the ZIF-67 and BIF-66 matrices by incipient wetness impregnation. Au@ZIF-67 and Au@BIF-66 hybrids were studied for the first time in the liquid phase hydroamination of phenylacetylene with aniline in an air atmosphere and have shown high activity and selectivity in respect to imine in this process. The pronounced impact of the nature of the metal-organic carrier, Au source, and reducing agent on the catalytic performance of the synthesized nanomaterials was found. To the best of our knowledge, it is the first example of using the zeolitic imidazolate framework and boron-imidazolate framework as the components of the gold-containing catalytic systems for the alkyne hydroamination.

Keywords: boron imidazolate frameworks; gold nanoparticles; heterogeneous catalysts; hybrid nanomaterials; intermolecular hydroamination; zeolitic imidazolate frameworks.