Nickel(I) Aryl Species

Synthesis, Properties, and Catalytic Activity

Megan Mohadjer Beromi, Gourab Banerjee, Gary W Brudvig, Nilay Hazari, Brandon Q. Mercado

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

In this work, Ni(I) aryl species that are directly relevant to cross-coupling have been synthesized. Transmetalation of (dppf)NiIX (dppf = 1,1′-bis(diphenylphosphino)-ferrocene, X = Cl, Br) with aryl Grignard reagents or aryl boronic acids in the presence of base produces Ni(I) aryl species of the form (dppf)NiI(Ar) (Ar = Ph, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, 2,4,6-iPr3C6H2). The stability of the Ni(I) aryl species is inversely correlated to the steric bulk on the aryl ligand. The most unstable Ni(I) aryl species are the most active precatalysts for Suzuki-Miyaura reactions because they rapidly decompose to generate the active Ni(0) catalyst. This study shows that Ni(I) aryl species are initially formed in the activation of Ni(I) halide precatalysts for Suzuki-Miyaura reactions and establishes their stoichiometric and catalytic reactivity profile.

Original languageEnglish
Pages (from-to)2526-2533
Number of pages8
JournalACS Catalysis
Volume8
Issue number3
DOIs
Publication statusPublished - Mar 2 2018

Fingerprint

Boronic Acids
Nickel
Catalyst activity
Chemical activation
Ligands
Catalysts
Acids
ferrocene

Keywords

  • cross-coupling
  • homogeneous catalysis
  • inorganic synthesis
  • mechanism
  • nickel

ASJC Scopus subject areas

  • Catalysis

Cite this

Mohadjer Beromi, M., Banerjee, G., Brudvig, G. W., Hazari, N., & Mercado, B. Q. (2018). Nickel(I) Aryl Species: Synthesis, Properties, and Catalytic Activity. ACS Catalysis, 8(3), 2526-2533. https://doi.org/10.1021/acscatal.8b00546

Nickel(I) Aryl Species : Synthesis, Properties, and Catalytic Activity. / Mohadjer Beromi, Megan; Banerjee, Gourab; Brudvig, Gary W; Hazari, Nilay; Mercado, Brandon Q.

In: ACS Catalysis, Vol. 8, No. 3, 02.03.2018, p. 2526-2533.

Research output: Contribution to journalArticle

Mohadjer Beromi, M, Banerjee, G, Brudvig, GW, Hazari, N & Mercado, BQ 2018, 'Nickel(I) Aryl Species: Synthesis, Properties, and Catalytic Activity', ACS Catalysis, vol. 8, no. 3, pp. 2526-2533. https://doi.org/10.1021/acscatal.8b00546
Mohadjer Beromi, Megan ; Banerjee, Gourab ; Brudvig, Gary W ; Hazari, Nilay ; Mercado, Brandon Q. / Nickel(I) Aryl Species : Synthesis, Properties, and Catalytic Activity. In: ACS Catalysis. 2018 ; Vol. 8, No. 3. pp. 2526-2533.
@article{3fe72f93b3144f0980b8f8eccd2ba5f5,
title = "Nickel(I) Aryl Species: Synthesis, Properties, and Catalytic Activity",
abstract = "In this work, Ni(I) aryl species that are directly relevant to cross-coupling have been synthesized. Transmetalation of (dppf)NiIX (dppf = 1,1′-bis(diphenylphosphino)-ferrocene, X = Cl, Br) with aryl Grignard reagents or aryl boronic acids in the presence of base produces Ni(I) aryl species of the form (dppf)NiI(Ar) (Ar = Ph, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, 2,4,6-iPr3C6H2). The stability of the Ni(I) aryl species is inversely correlated to the steric bulk on the aryl ligand. The most unstable Ni(I) aryl species are the most active precatalysts for Suzuki-Miyaura reactions because they rapidly decompose to generate the active Ni(0) catalyst. This study shows that Ni(I) aryl species are initially formed in the activation of Ni(I) halide precatalysts for Suzuki-Miyaura reactions and establishes their stoichiometric and catalytic reactivity profile.",
keywords = "cross-coupling, homogeneous catalysis, inorganic synthesis, mechanism, nickel",
author = "{Mohadjer Beromi}, Megan and Gourab Banerjee and Brudvig, {Gary W} and Nilay Hazari and Mercado, {Brandon Q.}",
year = "2018",
month = "3",
day = "2",
doi = "10.1021/acscatal.8b00546",
language = "English",
volume = "8",
pages = "2526--2533",
journal = "ACS Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",
number = "3",

}

TY - JOUR

T1 - Nickel(I) Aryl Species

T2 - Synthesis, Properties, and Catalytic Activity

AU - Mohadjer Beromi, Megan

AU - Banerjee, Gourab

AU - Brudvig, Gary W

AU - Hazari, Nilay

AU - Mercado, Brandon Q.

PY - 2018/3/2

Y1 - 2018/3/2

N2 - In this work, Ni(I) aryl species that are directly relevant to cross-coupling have been synthesized. Transmetalation of (dppf)NiIX (dppf = 1,1′-bis(diphenylphosphino)-ferrocene, X = Cl, Br) with aryl Grignard reagents or aryl boronic acids in the presence of base produces Ni(I) aryl species of the form (dppf)NiI(Ar) (Ar = Ph, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, 2,4,6-iPr3C6H2). The stability of the Ni(I) aryl species is inversely correlated to the steric bulk on the aryl ligand. The most unstable Ni(I) aryl species are the most active precatalysts for Suzuki-Miyaura reactions because they rapidly decompose to generate the active Ni(0) catalyst. This study shows that Ni(I) aryl species are initially formed in the activation of Ni(I) halide precatalysts for Suzuki-Miyaura reactions and establishes their stoichiometric and catalytic reactivity profile.

AB - In this work, Ni(I) aryl species that are directly relevant to cross-coupling have been synthesized. Transmetalation of (dppf)NiIX (dppf = 1,1′-bis(diphenylphosphino)-ferrocene, X = Cl, Br) with aryl Grignard reagents or aryl boronic acids in the presence of base produces Ni(I) aryl species of the form (dppf)NiI(Ar) (Ar = Ph, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, 2,4,6-iPr3C6H2). The stability of the Ni(I) aryl species is inversely correlated to the steric bulk on the aryl ligand. The most unstable Ni(I) aryl species are the most active precatalysts for Suzuki-Miyaura reactions because they rapidly decompose to generate the active Ni(0) catalyst. This study shows that Ni(I) aryl species are initially formed in the activation of Ni(I) halide precatalysts for Suzuki-Miyaura reactions and establishes their stoichiometric and catalytic reactivity profile.

KW - cross-coupling

KW - homogeneous catalysis

KW - inorganic synthesis

KW - mechanism

KW - nickel

UR - http://www.scopus.com/inward/record.url?scp=85042924565&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85042924565&partnerID=8YFLogxK

U2 - 10.1021/acscatal.8b00546

DO - 10.1021/acscatal.8b00546

M3 - Article

VL - 8

SP - 2526

EP - 2533

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 3

ER -