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.
N1 - Funding Information:
N.H. acknowledges support from the NIHGMS under Award Number R01GM120162. M.M. thanks the NSF for support as an NSF Graduate Research Fellow. The EPR spectroscopy work was supported by the Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences grant DE-FG02-05ER15646 (G.B. and G.W.B.). N.H. is a Camille and Henry-Dreyfus Foundation Teacher Scholar.
Publisher Copyright:
© 2018 American Chemical Society.
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
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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 -