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 language | English |
|---|---|
| Pages (from-to) | 2526-2533 |
| Number of pages | 8 |
| Journal | ACS Catalysis |
| Volume | 8 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - Mar 2 2018 |
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Keywords
- cross-coupling
- homogeneous catalysis
- inorganic synthesis
- mechanism
- nickel
ASJC Scopus subject areas
- Catalysis
Cite this
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 journal › Article
}
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
AN - SCOPUS:85042924565
VL - 8
SP - 2526
EP - 2533
JO - ACS Catalysis
JF - ACS Catalysis
SN - 2155-5435
IS - 3
ER -