Reversible oxidative insertion of a C=C bond into magnesium(I) dimers: generation of highly active 1,2-dimagnesioethane compounds

Aaron Boutland; Ashlea Carroll; Carlos Lamsfus; Andreas Stasch; Laurent Maron; Cameron Jones

doi:10.1021/jacs.7b11368

Reversible oxidative insertion of a C=C bond into magnesium(I) dimers: generation of highly active 1,2-dimagnesioethane compounds

Aaron Boutland, Ashlea Carroll, Carlos Lamsfus, Andreas Stasch, Laurent Maron, Cameron Jones

School of Chemistry

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

Abstract

The oxidative insertion of 1,1-diphenylethylene into the Mg-Mg bond of two magnesium(I) dimers, [(^ArNacnac)Mg−]₂ (Ar = C₆H₂Me₃-2,4,6 (Mes); C₆H₃Et₂-2,6; R = Et (Dep)), yielding 1,2-dimagnesioethane products, [{(ArNacnac)Mg}₂(μ-CH₂CPh₂)], is described. These reactions are readily reversible at room temperature, proceeding via reductive elimination of the olefin. Thus, the reactions represent the first examples of room temperature reversible redox processes for s-block metal complexes. The 1,2-dimagnesioethane products are highly activated magnesium alkyls, and show unprecedented, uncatalyzed reactivity towards, H₂, CO and ethylene. Computational studies have investigated the mechanisms of all presented reaction types.

Original language	English
Pages (from-to)	18190-18193
Journal	Journal of the American Chemical Society
Volume	139
Issue number	50
Early online date	5 Dec 2017
DOIs	https://doi.org/10.1021/jacs.7b11368
Publication status	Published - 20 Dec 2017

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MgMg_DPE_paper
Copyright © 2017 American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/jacs.7b11368
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@article{a766f7d4e1a349c4a3d47a46cb721757,

title = "Reversible oxidative insertion of a C=C bond into magnesium(I) dimers: generation of highly active 1,2-dimagnesioethane compounds",

abstract = "The oxidative insertion of 1,1-diphenylethylene into the Mg-Mg bond of two magnesium(I) dimers, [(ArNacnac)Mg−]2 (Ar = C6H2Me3-2,4,6 (Mes); C6H3Et2-2,6; R = Et (Dep)), yielding 1,2-dimagnesioethane products, [{(ArNacnac)Mg}2(μ-CH2CPh2)], is described. These reactions are readily reversible at room temperature, proceeding via reductive elimination of the olefin. Thus, the reactions represent the first examples of room temperature reversible redox processes for s-block metal complexes. The 1,2-dimagnesioethane products are highly activated magnesium alkyls, and show unprecedented, uncatalyzed reactivity towards, H2, CO and ethylene. Computational studies have investigated the mechanisms of all presented reaction types.",

author = "Aaron Boutland and Ashlea Carroll and Carlos Lamsfus and Andreas Stasch and Laurent Maron and Cameron Jones",

note = "Financial support from the Australian Research Council (CJ), the U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-14-1-4043 to CJ), The Humboldt Foundation (LM), the Chinese academy of Science (LM), is acknowledged.",

year = "2017",

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doi = "10.1021/jacs.7b11368",

language = "English",

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pages = "18190--18193",

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T1 - Reversible oxidative insertion of a C=C bond into magnesium(I) dimers

T2 - generation of highly active 1,2-dimagnesioethane compounds

AU - Boutland, Aaron

AU - Carroll, Ashlea

AU - Lamsfus, Carlos

AU - Stasch, Andreas

AU - Maron, Laurent

AU - Jones, Cameron

N1 - Financial support from the Australian Research Council (CJ), the U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-14-1-4043 to CJ), The Humboldt Foundation (LM), the Chinese academy of Science (LM), is acknowledged.

PY - 2017/12/20

Y1 - 2017/12/20

N2 - The oxidative insertion of 1,1-diphenylethylene into the Mg-Mg bond of two magnesium(I) dimers, [(ArNacnac)Mg−]2 (Ar = C6H2Me3-2,4,6 (Mes); C6H3Et2-2,6; R = Et (Dep)), yielding 1,2-dimagnesioethane products, [{(ArNacnac)Mg}2(μ-CH2CPh2)], is described. These reactions are readily reversible at room temperature, proceeding via reductive elimination of the olefin. Thus, the reactions represent the first examples of room temperature reversible redox processes for s-block metal complexes. The 1,2-dimagnesioethane products are highly activated magnesium alkyls, and show unprecedented, uncatalyzed reactivity towards, H2, CO and ethylene. Computational studies have investigated the mechanisms of all presented reaction types.

AB - The oxidative insertion of 1,1-diphenylethylene into the Mg-Mg bond of two magnesium(I) dimers, [(ArNacnac)Mg−]2 (Ar = C6H2Me3-2,4,6 (Mes); C6H3Et2-2,6; R = Et (Dep)), yielding 1,2-dimagnesioethane products, [{(ArNacnac)Mg}2(μ-CH2CPh2)], is described. These reactions are readily reversible at room temperature, proceeding via reductive elimination of the olefin. Thus, the reactions represent the first examples of room temperature reversible redox processes for s-block metal complexes. The 1,2-dimagnesioethane products are highly activated magnesium alkyls, and show unprecedented, uncatalyzed reactivity towards, H2, CO and ethylene. Computational studies have investigated the mechanisms of all presented reaction types.

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DO - 10.1021/jacs.7b11368

M3 - Article

SN - 0002-7863

VL - 139

SP - 18190

EP - 18193

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 50

ER -

Reversible oxidative insertion of a C=C bond into magnesium(I) dimers: generation of highly active 1,2-dimagnesioethane compounds

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