Oxidative Addition and β-Hydride Elimination by a Macrocyclic Dinickel Complex: Observing Bimetallic Elementary Reactions

Andie R. Delaney; Asja A. Kroeger; Michelle L. Coote; Annie L. Colebatch

doi:10.1002/chem.202302366

Oxidative Addition and β-Hydride Elimination by a Macrocyclic Dinickel Complex: Observing Bimetallic Elementary Reactions

Andie R. Delaney, Asja A. Kroeger, Michelle L. Coote^*, Annie L. Colebatch^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

The dinickel(I) complex Ni₂(^tBuPONNOPONNO), featuring a planar macrocyclic diphosphoranide ligand ^tBuPONNOPONNO, offers a unique architectural platform for observing bimetallic elementary reactions. Oxidative addition reactions of alkyl halides produce dinickel(II) complexes of the type Ni₂(μ-R)(μ-X)(^tBuPONNOPONNO). However, when R=Et β-hydride elimination is observed to form a dinickel monohydride, with the rate dependent on the nature of X. DFT studies suggest a new mechanism for bimetallic β-hydride elimination, where the rate dependence arises from the steric pressure imposed by the X group on the opposing trans face of the dinickel macrocycle. This work enhances understanding of bimetallic elementary reactions, particularly β-hydride elimination, which have not been well-explored for dinuclear systems.

Original language	English
Article number	e202302366
Journal	Chemistry - A European Journal
Volume	29
Issue number	67
DOIs	https://doi.org/10.1002/chem.202302366
Publication status	Published - 1 Dec 2023

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@article{00c76b1e5fd542b5b63fdd0d210091e7,

title = "Oxidative Addition and β-Hydride Elimination by a Macrocyclic Dinickel Complex: Observing Bimetallic Elementary Reactions",

abstract = "The dinickel(I) complex Ni2(tBuPONNOPONNO), featuring a planar macrocyclic diphosphoranide ligand tBuPONNOPONNO, offers a unique architectural platform for observing bimetallic elementary reactions. Oxidative addition reactions of alkyl halides produce dinickel(II) complexes of the type Ni2(μ-R)(μ-X)(tBuPONNOPONNO). However, when R=Et β-hydride elimination is observed to form a dinickel monohydride, with the rate dependent on the nature of X. DFT studies suggest a new mechanism for bimetallic β-hydride elimination, where the rate dependence arises from the steric pressure imposed by the X group on the opposing trans face of the dinickel macrocycle. This work enhances understanding of bimetallic elementary reactions, particularly β-hydride elimination, which have not been well-explored for dinuclear systems.",

keywords = "bimetallic, naphthyridine, nickel, oxidative addition, β-hydride elimination",

author = "Delaney, {Andie R.} and Kroeger, {Asja A.} and Coote, {Michelle L.} and Colebatch, {Annie L.}",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2023",

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doi = "10.1002/chem.202302366",

language = "English",

volume = "29",

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T1 - Oxidative Addition and β-Hydride Elimination by a Macrocyclic Dinickel Complex

T2 - Observing Bimetallic Elementary Reactions

AU - Delaney, Andie R.

AU - Kroeger, Asja A.

AU - Coote, Michelle L.

AU - Colebatch, Annie L.

PY - 2023/12/1

Y1 - 2023/12/1

N2 - The dinickel(I) complex Ni2(tBuPONNOPONNO), featuring a planar macrocyclic diphosphoranide ligand tBuPONNOPONNO, offers a unique architectural platform for observing bimetallic elementary reactions. Oxidative addition reactions of alkyl halides produce dinickel(II) complexes of the type Ni2(μ-R)(μ-X)(tBuPONNOPONNO). However, when R=Et β-hydride elimination is observed to form a dinickel monohydride, with the rate dependent on the nature of X. DFT studies suggest a new mechanism for bimetallic β-hydride elimination, where the rate dependence arises from the steric pressure imposed by the X group on the opposing trans face of the dinickel macrocycle. This work enhances understanding of bimetallic elementary reactions, particularly β-hydride elimination, which have not been well-explored for dinuclear systems.

AB - The dinickel(I) complex Ni2(tBuPONNOPONNO), featuring a planar macrocyclic diphosphoranide ligand tBuPONNOPONNO, offers a unique architectural platform for observing bimetallic elementary reactions. Oxidative addition reactions of alkyl halides produce dinickel(II) complexes of the type Ni2(μ-R)(μ-X)(tBuPONNOPONNO). However, when R=Et β-hydride elimination is observed to form a dinickel monohydride, with the rate dependent on the nature of X. DFT studies suggest a new mechanism for bimetallic β-hydride elimination, where the rate dependence arises from the steric pressure imposed by the X group on the opposing trans face of the dinickel macrocycle. This work enhances understanding of bimetallic elementary reactions, particularly β-hydride elimination, which have not been well-explored for dinuclear systems.

KW - bimetallic

KW - naphthyridine

KW - nickel

KW - oxidative addition

KW - β-hydride elimination

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U2 - 10.1002/chem.202302366

DO - 10.1002/chem.202302366

M3 - Article

SN - 0947-6539

VL - 29

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 67

M1 - e202302366

ER -

Oxidative Addition and β-Hydride Elimination by a Macrocyclic Dinickel Complex: Observing Bimetallic Elementary Reactions

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