Abstract
Sodium reduction of [{SiNDipp}Mg] [{SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3] provides the Mg(I) species, [{SiNDipp}MgNa]2, in which the long Mg–Mg bond (>3.2 Å) is augmented by persistent Na–aryl interactions. Computational assessment indicates that this molecule is best considered to comprise a contiguous tetrametallic core, a viewpoint borne out by its reaction with CO, which results in ethynediolate formation mediated by the dissimilar metal centers.
Highlights
Prior to Jones and co-workers’ isolation of stable guanidinate and β-diketiminate (BDI) derivatives such as compound 1 in 2007 (Chart 1),[1−5] experimental studies of low oxidation state Chart 1
A large region of negative Laplacian in the Mg−Mg internuclear region comprises a non-nuclear attractor (NNA) containing 0.8 electrons, in effect electron density that is not associated with a particular nucleus and, distinct from the positions of the magnesium atoms.[9,18−20]
Prompted by the robust nature of compounds 4 and 7, in this contribution we show that the thermodynamic preference for heavier group 1 element−aryl interactions[29,30] can provide a strategy to access dinuclear low oxidation state alkaline earth species that circumvents conventional salt elimination
Summary
Prior to Jones and co-workers’ isolation of stable guanidinate and β-diketiminate (BDI) derivatives such as compound 1 in 2007 (Chart 1),[1−5] experimental studies of low oxidation state Chart 1. Initial DFT calculations were performed to model the sodium and potassium reduction of a neutral magnesium derivative, [{SiNDipp}Mg](8), supported by the amide ligand utilized in compound 7.
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