Intermolecular Oxidative Addition of Aryl Halides to Platinum(II) Alkyl Complexes

2019 ◽  
Vol 38 (10) ◽  
pp. 2273-2277 ◽  
Author(s):  
Kristof M. Altus ◽  
Eric G. Bowes ◽  
D. Dawson Beattie ◽  
Jennifer A. Love
Keyword(s):  
Oxidative Addition ◽  
Aryl Halides ◽  
Alkyl Complexes

Intermolecular Oxidative Addition of Aryl Halides to Platinum(II) Alkyl Complexes

2018 ◽  
Author(s):  
Kristof Altus ◽  
Eric Bowes ◽  
D. Dawson Beattie ◽  
Jennifer Love
Keyword(s):  
Aryl Halide ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Aryl Halides ◽  
Alkyl Complexes ◽  
Species Isolation

We report the first well-defined example of intermolecular aryl halide oxidative addition (OA) to Pt(II). Complexes of the type (IMes)PtMe<sub>2</sub>(L) and (IMes’)PtMe(L) (L = SMe<sub>2</sub>, pyridine; IMes = <i>N,N</i>-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IMes’ = cyclometalated IMes) undergo intermolecular OA of phenyl iodide (PhI) at 60 °C, producing toluene <i>via</i> reductive elimination from a proposed Pt(IV)-phenyl species. Isolation of a model Pt(IV) OA product provides evidence for a Pt(II)/(IV) pathway. The OA of PhI is not limited to Pt(II)-IMes complexes;analogous reactions also proceed with phosphine-ligated Pt(II) dialkyl complexes, demonstrating that this reaction is feasible for a variety of electron-rich Pt(II) complexes bearing labile ligands.

Intermolecular Oxidative Addition of Aryl Halides to Platinum(II) Alkyl Complexes

2018 ◽  
Author(s):  
Kristof Altus ◽  
Eric Bowes ◽  
D. Dawson Beattie ◽  
Jennifer Love
Keyword(s):  
Aryl Halide ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Aryl Halides ◽  
Alkyl Complexes ◽  
Species Isolation

We report the first well-defined example of intermolecular aryl halide oxidative addition (OA) to Pt(II). Complexes of the type (IMes)PtMe<sub>2</sub>(L) and (IMes’)PtMe(L) (L = SMe<sub>2</sub>, pyridine; IMes = <i>N,N</i>-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IMes’ = cyclometalated IMes) undergo intermolecular OA of phenyl iodide (PhI) at 60 °C, producing toluene <i>via</i> reductive elimination from a proposed Pt(IV)-phenyl species. Isolation of a model Pt(IV) OA product provides evidence for a Pt(II)/(IV) pathway. The OA of PhI is not limited to Pt(II)-IMes complexes;analogous reactions also proceed with phosphine-ligated Pt(II) dialkyl complexes, demonstrating that this reaction is feasible for a variety of electron-rich Pt(II) complexes bearing labile ligands.

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

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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