Sodium magnesiate

Donor-Free Homo- and Heteroleptic Sodium Magnesiate Complexes... 

The homoleptic sodium magnesiate 27 (Fig. 20) represents the first example of a structurally characterized solvent-free tris-alkyl version reported in the frterature. Complex 27 exists as a polymeric ate— prepared by a co-complexation approach by mixing the monometaUic alkyls [NaCH2SiMe3] and [Mg(CH2SiMe3)] in an -hexane/toluene solvent... 

The bis(amido) alkyl sodium magnesiate [NaMg(HMDS)2("Bu)]oo 28 (Fig. 20C) is also polymeric however, it adopts a one-dimensional chainlike infinite polymer through an almost linear Na—C( Bu)-Mg bridge. Two... 

Na and Mg atoms, an exceptionally rare structural feature in the chemistry of sodium magnesiates. 

Fig. 32 Molecular structure of the sodium magnesiate 49. THF molecules form the [Na (THF)2] and [NafTHFjs]" units have been omitted for clarity.

The donor-firee sodium magnesiate complexes with general formula [Na4Mg2(TMP)6(arene-di-ide)] (arene-di-ide = 2,5-C6H30Me in 54 3,5-C6H3NMe2 in 55 and 3,5-C6H3Me in 56 Fig. 35) are representative examples of inverse crown complexes." " Those complexes are coined inverse crowns in view of their topological but inverse relation to conventional crown ethers in... 

Francos J, Fleming BJ, Garcia-Alvarez P, et al. Complexity in seemingly simple sodium magnesiate systems. Dalton Trans. 2014 43(38) 14424—14431. 

Heman-Gomez A, Bradley TD, Kennedy AR, Livingstone Z, Robertson SD, Hevia E. Developing catalytic applications of cooperative bimetallics competitive hydroamination/trimerization reactions of isocyanates catalysed by sodium magnesiates. Chem Commun. 2013 49(77) 8659—8661. 

Kennedy AR, O Hara CT. Isolation and characterisation of a (—)-sparteine coordinated mixedalkyl/amido sodium magnesiate, a chiral variant of an important utihty ate base. Dalton Trans. 2008 (37) 4975-4977. 

Fig. 40 Cleave and capture chemistry executed by a sodium magnesiate on the cyclic ether THF...

Fig. 41 Cascade reaction of a sodium magnesiate towards the important heterocycle benzothiazole...

Studying these reactions in solution by quenching with electrophilic iodine revealed that while the weta-metalated product was the major product (73%), a small amount of ortho-metalation (6%) and para-metalation (21%) had also occurred [62]. The wefa-metalation of toluene can also be accomplished using the heteroleptic sodium magnesiate TMEDA-Na(TMP)(nBu)Mg(TMP) (Fig. 16) [63]. This base operates synergically via overall alkyl basicity to yield a discrete molecular framework containing a bridging molecule of toluene, metalated at the meta position [64]. 

A slight modification of the sodium magnesiate has a profound effect on how the metalation of benzene is manifested. Specifically, the heteroleptic ate with a Lewis... 

Fig. 28 Amide dependence of magnesiation of ferrocene with sodium magnesiate...

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