Stable Magnesium(I) Compounds with Mg-Mg Bonds

Abstract

The chemistry of the group 2 metals (beryllium, magnesium, calcium, strontium, and barium) is dominated by the +2 oxidation state. Here, we report the reductions of two magnesium(II) iodide complexes with potassium metal in toluene, leading to thermally stable magnesium(I) compounds, (L)MgMg(L) (where L is [(Ar)NC(NPri2)N(Ar)]- or {[(Ar)NC(Me)]2CH}-, Ar is 2,6-diisopropylphenyl, Me is methyl, and Pri is isopropyl) in moderate yields. The results of x-ray crystallographic and theoretical studies are consistent with central Mg2+(2) units that have single, covalent magnesium-magnesium bonding interactions with 2.8508 +/- 0.0012 (standard deviation) and 2.8457 +/- 0.0008 angstrom bond lengths, respectively, and predominantly ionic interactions with the anionic ligands (L).

A multicentre-bonded [ZnI]8 cluster with cubic aromaticity

“…cube are formed through overlap of the 4s orbitals, with slight mixing from the Zn 4p and Zn 3d orbitals. Among them, four bonding orbitals with a 1g and t 1u symmetry are fully occupied, giving a ground-state electronic configuration of (a 1g ) 2 (t 1u ) 6 , whereas four antibonding orbitals with t 2g and a 2u symmetry are completely empty. The bonding pattern of the eight MOs is comparable to those of Au 3 þ and benzene molecules that have the famous planar s-and p-aromaticity 34 and obey Hückel's 4n þ 2 rule (Supplementary Fig.…”

Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium

“…With some recent remarkable exceptions (Green et al 2007(Green et al , 2008Bonyhady et al 2009;Krieck et al 2009), the organometallic compounds of the heavy alkaline earths are overwhelmingly redox inactive species, which demonstrate a +2 oxidation state. The M 2+ cations achieve noble gas configurations, and compounds of the heavy metals possess a d 0 electron configuration.…”

Photochemical Route to Actinide-Transition Metal Bonds: Synthesis, Characterization and Reactivity of a Series of Thorium and Uranium Heterobimetallic Complexes

“…12 In spite of this, f-element metal-metal bonds are still rare in comparison to the multitude of examples for the s, p and d block. [13][14][15] This is due in part to the fact that while there are a broad range of synthetic routes to metal-metal bonds involving transition metals in particular, 15 the synthesis of actinide analogues has been limited to salt metathesis and elimination reactions. Accordingly, only 17 structurally characterized examples have been reported, 16 establishing uranium bound to iron, ruthenium, rhenium and cobalt, in addition to the first example involving thorium.…”