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Web Date: April 7, 2014

Mixing And Matching Metals

Organometallics: Chemists Create An Inorganic Grignard Reagent To Forge Metal-Metal Bonds
Department: Science & Technology
News Channels: Materials SCENE, Organic SCENE, JACS In C&EN
Keywords: Grignard reagent, multiple bonding, bimetallic, metal-metal bond
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A manganese-magnesium inorganic Grignard complex.
Credit: Cameron Jones
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A manganese-magnesium inorganic Grignard complex.
Credit: Cameron Jones

An international research team has reported some surprising new metal-metal bonded complexes—sought after as catalysts and enzyme mimics—including an unprecedented Mn(0)–Mg(II) species that serves as an inorganic version of a Grignard reagent.

The team led by Cameron Jones of Monash University, in Victoria, Australia, initially was attempting to prepare a Mn–Mn complex using a Mg(I) complex as a reagent. But the researchers discovered they had made the mixed-metal LMn–MgL' instead, where L and L' are enormous amide ligands that defy naming (J. Am. Chem. Soc. 2014, DOI: 10.1021/ja5021348). Jones and his colleagues then used the deep-blue Mn–Mg species to make Mn(I)–Mn(I) and Mn(II)–Cr(0) complexes.

Normal Grignard reagents are organomagnesium compounds widely used in organic synthesis to transfer an organic group from magnesium to an organic molecule. In an analogous way, an inorganic Grignard reagent transfers a metal and its ligand from magnesium to another metal complex, resulting in a new bimetallic compound. The concept of inorganic Grignard reagents was developed in the 1970s, but few examples have been reported and the reagents and products were never well defined.

“Controlled access to heterometallics, especially when the metal ions are electronically similar, can be quite challenging,” says Connie C. Lu of the University of Minnesota, Twin Cities, whose group studies multiply bonded bimetallic complexes. “Using inorganic Grignard reagents is a neat strategy that’s currently not being exploited in the field of metal-metal bonding.”

Of interest to inorganic chemists, the new Mn species are the first examples of two-coordinate Mn complexes. Most transition metals typically require coordination via four or more bonds for stability. The bulky amide ligands restrict access to metal coordination sites, forcing the metals to stabilize in lower oxidation states than usual based on their complement of valence electrons and therefore with fewer ligands. In addition, preliminary reactions with O2, N2O, and a carbodiimide suggest that the new Mn(0)–Mg(II) complex can serve as a strong reducing agent for organic synthesis.

 
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ISSN 0009-2347
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