Strongly reducing magnesium(0) complexes

B. Rösch, T. X. Gentner, J. Eyselein, J. Langer, H. Elsen and S. Harder ()
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B. Rösch: Friedrich-Alexander University Erlangen-Nürnberg
T. X. Gentner: Friedrich-Alexander University Erlangen-Nürnberg
J. Eyselein: Friedrich-Alexander University Erlangen-Nürnberg
J. Langer: Friedrich-Alexander University Erlangen-Nürnberg
H. Elsen: Friedrich-Alexander University Erlangen-Nürnberg
S. Harder: Friedrich-Alexander University Erlangen-Nürnberg

Nature, 2021, vol. 592, issue 7856, 717-721

Abstract: Abstract A complex of a metal in its zero oxidation state can be considered a stabilized, but highly reactive, form of a single metal atom. Such complexes are common for the more noble transition metals. Although rare examples are known for electronegative late-main-group p-block metals or semimetals1–6, it is a challenge to isolate early-main-group s-block metals in their zero oxidation state7–11. This is directly related to their very low electronegativity and strong tendency to oxidize. Here we present examples of zero-oxidation-state magnesium (that is, magnesium(0)) complexes that are stabilized by superbulky, monoanionic, β-diketiminate ligands. Whereas the reactivity of an organomagnesium compound is typically defined by the nucleophilicity of its organic groups and the electrophilicity of Mg2+ cations, the Mg0 complexes reported here feature electron-rich Mg centres that are nucleophilic and strongly reducing. The latter property is exemplified by the ability to reduce Na+ to Na0. We also present a complex with a linear Mg3 core that formally could be described as a MgI–Mg0–MgI unit. Such multinuclear mixed-valence Mgn clusters are discussed as fleeting intermediates during the early stages of Grignard reagent formation. Their remarkably strong reducing power implies a rich reactivity and application as specialized reducing agents.

Date: 2021
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DOI: 10.1038/s41586-021-03401-w

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