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Inorganic Chemistry

Zeroing in on magnesium

Chemists make the first stable Mg(0) complexes

by Bethany Halford
May 2, 2021 | A version of this story appeared in Volume 99, Issue 16

A magnesium(0) complex has bulky ligands and magnesium-sodium bonds.
Credit: Adapted from Nature

Like most of the elements in the periodic table’s second column, magnesium eagerly gives away a couple of electrons to achieve a full outer shell and a +2 oxidation state. For the first time, chemists have maneuvered magnesium into a stable complex (shown) where it possesses all its electrons (Nature 2021, DOI: 10.1038/s41586-021-03401-w). Sjoerd Harder and colleagues at Friedrich Alexander University Erlangen-Nuremberg accomplished this feat with the help of bulky β-diketiminate ligands. To make the Mg(0) complex, the chemists reduced ligand-bound Mg2+ with fine sodium metal. As a result, the complex contains the first observed Mg–Na bonds. Although the complex is moderately stable at room temperature, it is highly reactive, readily reducing Na ions to Na metal and breaking H2 as well as a C–F bond. When dissolved in benzene, the Mg(0) complex slowly decomposes to form a structure with a linear Mg3 core. The researchers suggest that such Mg metal clusters might be fleeting intermediates in the formation of Grignard reagents, which have been synthetic tools for more than a century even though their formation remains something of a mystery.


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