Reductive Trimerization of CO to the Deltate Dianion Using Activated Magnesium(I) Compounds - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Journal of the American Chemical Society Year : 2019

Reductive Trimerization of CO to the Deltate Dianion Using Activated Magnesium(I) Compounds

Abstract

This study details syntheses of unsymmetrical magnesium(I) adduct complexes, [((Ar)Nacnac)-(D)Mg-Mg ((Ar)Nacnac)] ((Ar)Nacnac = [(ArNC-Me)(2)CH](-)), Ar = xylyl (Xyl), mesityl (Mes), 2,6-diethylphenyl (Dep), or 2,6-diisopropylphenyl (Dip); D = N-heterocyclic carbene or 4-dimethylaminopyridine, DMAP), which X-ray crystallographic studies show to have markedly elongated Mg-Mg bonds. Two of these highly reactive species are shown to reductively trimerize CO to yield rare crystallographically characterized examples of the planar, aromatic deltate dianion, incorporated in the complexes [{((DiP)Nacnac)(D)Mg(mu-C3O3)Mg((DiP)Nacnac)}(2)] (D = DMAP or :C{N(Me)C-(Me)}(2)). DFT calculations suggest that these complexes form via stepwise two-electron reductions of three CO molecules, resulting in the formation of three C C bonds within the cyclic deltate unit. This work highlights the utility of activated magnesium(I) adduct complexes as soluble organometallic models for the study of reductive C C bond-forming events in, for example, the heterogeneously catalyzed Fischer-Tropsch process.
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Dates and versions

hal-04022183 , version 1 (09-03-2023)

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K. Yuvaraj, Iskander Douair, Albert Paparo, Laurent Maron, Cameron Jones. Reductive Trimerization of CO to the Deltate Dianion Using Activated Magnesium(I) Compounds. Journal of the American Chemical Society, 2019, 141 (22), pp.8764-8768. ⟨10.1021/jacs.9b04085⟩. ⟨hal-04022183⟩
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