Recyclable and Reusable Heteroleptic Nickel Catalyst Immobilized on Metal-Organic Framework for Suzuki-Miyaura Coupling

Palani Elumalai, Hind Mamlouk, Wubulikasimu Yiming, Liang Feng, Shuai Yuan, Hong Cai Zhou, Sherzod Madrahimov

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Metal-organic frameworks (MOFs) provide highly versatile platforms to stabilize molecular catalysts that are not readily accessible under homogeneous conditions, thus enabling access to a new set of catalytic materials. Herein, we describe a recyclable and highly active nickel catalyst immobilized on MOF for Suzuki-Miyaura coupling reaction, which operates under mild conditions. This mixed ligand catalyst forms from the combination of 1 equiv of MOF-immobilized ligand, 1 equiv of nickel source, and 1 equiv of PPh3. The nature of the catalyst was verified through a series of analytical tests and catalysis experiments. The immobilized catalyst was reusable for at least up to 7 cycles without decrease in the yield of the coupled product. We also verified that this reaction does not work under homogeneous conditions and that the reaction is truly heterogeneous through "hot filtration" experiments. We identified that the reaction is first order in arylborane concentration and negative order in arylbromide concentration through the effect of substrate concentrations on the initial rate. This informed us to conduct the catalysis under slow addition of the arylbromide and reduce the catalyst loading to 1% from 3%, without detriment to the yield or rate of the reaction. The catalyst gave good to excellent isolated yields with a range of functionalities, including heterocycles on aryl bromide with widely varying electronic properties.

Original languageEnglish
Pages (from-to)41431-41438
Number of pages8
JournalACS Applied Materials and Interfaces
Volume10
Issue number48
DOIs
Publication statusPublished - 5 Dec 2018

Fingerprint

Nickel
Metals
Catalysts
Catalysis
Ligands
Bromides
Electronic properties
Experiments
Substrates

Keywords

  • C-C bond formation
  • metal-organic framework
  • MOF-immobilized heteroleptic catalyst
  • nickel-catalyst
  • Suzuki-Miyaura cross-coupling reaction

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Recyclable and Reusable Heteroleptic Nickel Catalyst Immobilized on Metal-Organic Framework for Suzuki-Miyaura Coupling. / Elumalai, Palani; Mamlouk, Hind; Yiming, Wubulikasimu; Feng, Liang; Yuan, Shuai; Zhou, Hong Cai; Madrahimov, Sherzod.

In: ACS Applied Materials and Interfaces, Vol. 10, No. 48, 05.12.2018, p. 41431-41438.

Research output: Contribution to journalArticle

Elumalai, Palani ; Mamlouk, Hind ; Yiming, Wubulikasimu ; Feng, Liang ; Yuan, Shuai ; Zhou, Hong Cai ; Madrahimov, Sherzod. / Recyclable and Reusable Heteroleptic Nickel Catalyst Immobilized on Metal-Organic Framework for Suzuki-Miyaura Coupling. In: ACS Applied Materials and Interfaces. 2018 ; Vol. 10, No. 48. pp. 41431-41438.
@article{32a570e4e4794559b2596f2e1cc2b70e,
title = "Recyclable and Reusable Heteroleptic Nickel Catalyst Immobilized on Metal-Organic Framework for Suzuki-Miyaura Coupling",
abstract = "Metal-organic frameworks (MOFs) provide highly versatile platforms to stabilize molecular catalysts that are not readily accessible under homogeneous conditions, thus enabling access to a new set of catalytic materials. Herein, we describe a recyclable and highly active nickel catalyst immobilized on MOF for Suzuki-Miyaura coupling reaction, which operates under mild conditions. This mixed ligand catalyst forms from the combination of 1 equiv of MOF-immobilized ligand, 1 equiv of nickel source, and 1 equiv of PPh3. The nature of the catalyst was verified through a series of analytical tests and catalysis experiments. The immobilized catalyst was reusable for at least up to 7 cycles without decrease in the yield of the coupled product. We also verified that this reaction does not work under homogeneous conditions and that the reaction is truly heterogeneous through {"}hot filtration{"} experiments. We identified that the reaction is first order in arylborane concentration and negative order in arylbromide concentration through the effect of substrate concentrations on the initial rate. This informed us to conduct the catalysis under slow addition of the arylbromide and reduce the catalyst loading to 1{\%} from 3{\%}, without detriment to the yield or rate of the reaction. The catalyst gave good to excellent isolated yields with a range of functionalities, including heterocycles on aryl bromide with widely varying electronic properties.",
keywords = "C-C bond formation, metal-organic framework, MOF-immobilized heteroleptic catalyst, nickel-catalyst, Suzuki-Miyaura cross-coupling reaction",
author = "Palani Elumalai and Hind Mamlouk and Wubulikasimu Yiming and Liang Feng and Shuai Yuan and Zhou, {Hong Cai} and Sherzod Madrahimov",
year = "2018",
month = "12",
day = "5",
doi = "10.1021/acsami.8b16136",
language = "English",
volume = "10",
pages = "41431--41438",
journal = "ACS Applied Materials and Interfaces",
issn = "1944-8244",
publisher = "American Chemical Society",
number = "48",

}

TY - JOUR

T1 - Recyclable and Reusable Heteroleptic Nickel Catalyst Immobilized on Metal-Organic Framework for Suzuki-Miyaura Coupling

AU - Elumalai, Palani

AU - Mamlouk, Hind

AU - Yiming, Wubulikasimu

AU - Feng, Liang

AU - Yuan, Shuai

AU - Zhou, Hong Cai

AU - Madrahimov, Sherzod

PY - 2018/12/5

Y1 - 2018/12/5

N2 - Metal-organic frameworks (MOFs) provide highly versatile platforms to stabilize molecular catalysts that are not readily accessible under homogeneous conditions, thus enabling access to a new set of catalytic materials. Herein, we describe a recyclable and highly active nickel catalyst immobilized on MOF for Suzuki-Miyaura coupling reaction, which operates under mild conditions. This mixed ligand catalyst forms from the combination of 1 equiv of MOF-immobilized ligand, 1 equiv of nickel source, and 1 equiv of PPh3. The nature of the catalyst was verified through a series of analytical tests and catalysis experiments. The immobilized catalyst was reusable for at least up to 7 cycles without decrease in the yield of the coupled product. We also verified that this reaction does not work under homogeneous conditions and that the reaction is truly heterogeneous through "hot filtration" experiments. We identified that the reaction is first order in arylborane concentration and negative order in arylbromide concentration through the effect of substrate concentrations on the initial rate. This informed us to conduct the catalysis under slow addition of the arylbromide and reduce the catalyst loading to 1% from 3%, without detriment to the yield or rate of the reaction. The catalyst gave good to excellent isolated yields with a range of functionalities, including heterocycles on aryl bromide with widely varying electronic properties.

AB - Metal-organic frameworks (MOFs) provide highly versatile platforms to stabilize molecular catalysts that are not readily accessible under homogeneous conditions, thus enabling access to a new set of catalytic materials. Herein, we describe a recyclable and highly active nickel catalyst immobilized on MOF for Suzuki-Miyaura coupling reaction, which operates under mild conditions. This mixed ligand catalyst forms from the combination of 1 equiv of MOF-immobilized ligand, 1 equiv of nickel source, and 1 equiv of PPh3. The nature of the catalyst was verified through a series of analytical tests and catalysis experiments. The immobilized catalyst was reusable for at least up to 7 cycles without decrease in the yield of the coupled product. We also verified that this reaction does not work under homogeneous conditions and that the reaction is truly heterogeneous through "hot filtration" experiments. We identified that the reaction is first order in arylborane concentration and negative order in arylbromide concentration through the effect of substrate concentrations on the initial rate. This informed us to conduct the catalysis under slow addition of the arylbromide and reduce the catalyst loading to 1% from 3%, without detriment to the yield or rate of the reaction. The catalyst gave good to excellent isolated yields with a range of functionalities, including heterocycles on aryl bromide with widely varying electronic properties.

KW - C-C bond formation

KW - metal-organic framework

KW - MOF-immobilized heteroleptic catalyst

KW - nickel-catalyst

KW - Suzuki-Miyaura cross-coupling reaction

UR - http://www.scopus.com/inward/record.url?scp=85057544166&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85057544166&partnerID=8YFLogxK

U2 - 10.1021/acsami.8b16136

DO - 10.1021/acsami.8b16136

M3 - Article

VL - 10

SP - 41431

EP - 41438

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

SN - 1944-8244

IS - 48

ER -