scholarly journals Steric effects determine the mechanisms of reactions between bis(N-heterocyclic carbene)-nickel(0) complexes and aryl halides

2018 ◽  
Vol 54 (75) ◽  
pp. 10646-10649 ◽  
Author(s):  
David J. Nelson ◽  
Feliu Maseras
Keyword(s):  
Oxidative Addition ◽  
Aryl Halides ◽  
Steric Effects ◽  
Dft Studies ◽  
Mechanisms Of Reactions

DFT studies show that [Ni(NHC)2] complexes with large ligands disfavour oxidative addition and instead react with aryl halides via halide abstraction.

Quantifying Steric Effects of α-Diimine Ligands. Oxidative Addition of MeI to Rhodium(I) and Migratory Insertion in Rhodium(III) Complexes

2003 ◽  
Vol 22 (5) ◽  
pp. 1047-1054 ◽  
Author(s):  
Luca Gonsalvi ◽  
Joseph A. Gaunt ◽  
Harry Adams ◽  
Aurora Castro ◽  
Glenn J. Sunley ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Steric Effects ◽  
Diimine Ligands ◽  
Migratory Insertion

Oxidative Addition of Aryl Halides to Transient Anionic à-Aryl–Palladium(0) Intermediates—Application to Palladium-Catalyzed Reductive Coupling of Aryl Halides

1996 ◽  
Vol 2 (8) ◽  
pp. 957-966 ◽  
Author(s):  
Christian Amatore ◽  
Emmanuelle Carré ◽  
Anny Jutand ◽  
Hideo Tanaka ◽  
Qinghua Ren ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Aryl Halides ◽  
Reductive Coupling ◽  
Palladium Catalyzed

Oxidative Addition of Propargyl Halides, Chloroacetonitrile, and Ethyl Chloroacetate to a Dimethylplatinum(II) Complex: Kinetic and DFT Studies

2014 ◽  
Vol 33 (7) ◽  
pp. 1689-1699 ◽  
Author(s):  
S. Jafar Hoseini ◽  
Hasan Nasrabadi ◽  
Roghayeh Hashemi Fath ◽  
Zohreh Moradi ◽  
Mehdi Rashidi
Keyword(s):  
Oxidative Addition ◽  
Dft Studies ◽  
Ethyl Chloroacetate

scholarly journals Oxidative Addition of Aryl Halides to a Ni(I)-Bipyridine Complex

2022 ◽  
Author(s):  
Stephen Ting ◽  
Wendy Williams ◽  
Abigail Doyle
Keyword(s):  
Oxidative Addition ◽  
Aryl Halides ◽  
Solution Phase ◽  
Nickel Catalysis ◽  
Mechanistic Studies ◽  
Redox Equilibrium ◽  
Aryl Bromides ◽  
First Time

The oxidative addition of aryl halides to bipyridine- or phenanthroline-ligated nickel(I) is a commonly proposed step in nickel catalysis. However, there is a scarcity of complexes of this type that both are well-defined and undergo oxidative addition with aryl halides, hampering organometallic studies of this process. We report the synthesis of a well-defined Ni(I) complex, [(CO2Etbpy)NiCl]4 (1). Its solution-phase speciation is characterized by a significant population of monomer and a redox equilibrium that can be perturbed by π-acceptors and σ-donors. 1 reacts readily with aryl bromides, and mechanistic studies are consistent with a mechanism proceeding through an initial Ni(I) → Ni(III) oxidative addition. Such a process was demonstrated stoichiometrically for the first time, affording a structurally characterized Ni(III) aryl complex.

scholarly journals Mechanochemistry allows carrying out sensitive organometallic reactions in air: glove-box-and-Schlenk-line-free synthesis of oxidative addition complexes from aryl halides and palladium(0)

2019 ◽  
Vol 10 (22) ◽  
pp. 5837-5842 ◽  
Author(s):  
Koji Kubota ◽  
Rina Takahashi ◽  
Hajime Ito
Keyword(s):  
Oxidative Addition ◽  
Aryl Halides ◽  
Organometallic Reactions ◽  
Wide Range

We have demonstrated that mechanochemistry allows synthesizing a wide range of palladium oxidative addition complexes in air.

Aldehydes and Ketones Influence Reactivity and Selectivity in Nickel-Catalyzed Suzuki-Miyaura Reactions

2019 ◽  
Author(s):  
Alasdair Cooper ◽  
David Leonard ◽  
Sonia Bajo ◽  
Paul Burton ◽  
David Nelson
Keyword(s):  
Carbonyl Group ◽  
Functional Groups ◽  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Aryl Halides ◽  
Cross Coupling Reaction ◽  
Site Selectivity ◽  
Aldehydes And Ketones ◽  
The Cross

We show that the energetically-favorable coordination of aldehydes and ketones – but not esters – to nickel(0) during Suzuki-Miyaura reactions can lead either to exquisite selectivity and enhanced reactivity, or to the inhibition<br>of the reaction. Aryl halides where the C-X bond is connected to the same π-system as an aldehyde or ketone functional<br>group undergo unexpectedly rapid oxidative addition, and are selectively cross-coupled during inter- and intramolecular<br>competition reactions. When aldehydes and ketones are present elsewhere, such as in the form of exogenous additives,<br>the cross-coupling reaction is inhibited depending on how strongly the pendant carbonyl group can coordinate to nickel(0). This work advances our understanding of how common functional groups interact with nickel(0) catalysts, and presents synthetic chemists with a tool that can be used to achieve site-selectivity in functionalized molecules. <br>

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