02003nas a2200193   4500008004100000022001400041245009200055210006900147260000800216300001200224490000700236520134500243100001901588700002501607700001701632700002401649700001901673856011701692       2025                        eng d  a0276-733300aMagnesium-ligand cooperation in breaking the O-H and C-H bonds of water and diazoalkane0 aMagnesiumligand cooperation in breaking the OH and CH bonds of w  cMAR  a875-8810 v443 a<p>
	In our previous paper, we reported that the reaction of a tridentate nacnac ligand with a pendant picolyl group, with KHMDS and MgI2, resulted in the formation of a homoleptic hexacoordinate magnesium compound. Here, we show that the analogous reaction of the ligand with CH3MgBr led to a heteroleptic magnesium bromide species (1). Attempts to generate the magnesium hydride species from 1 led to the dearomatization of the pyridine ring, and the resulting product was a magnesium hydroxide (3) presumably generated due to an adventitious amount of water. The reaction of the ligand with nBu2Mg afforded a unique dearomatized magnesium species (2) in high yield. Theoretical calculations reveal the presence of a nonbonding orbital on the magnesium, susceptible to nucleophilic attack. Indeed, the reaction of 2 with H2O/D2O cleaves the O-H/D bond via magnesium-ligand cooperation and generates a magnesium hydroxide (4 and 5). In addition, 2 reacts with Me3SiCHN2 and cleaves the C-H bond to generate another unusual, well-defined magnesium compound with a bridging isocyanide moiety (6) via migration of the SiMe3 group from the carbon to the nitrogen atom. The latter can be described as a dimer of magnesium isocyanamide. DFT calculations were performed to understand the electronic structures of the synthesized molecules.</p>
1 aSharma, Vishal1 aDash, Soumya, Ranjan1 aVanka, Kumar1 aGonnade, Rajesh, G.1 aSen, Sakya, S.  uhttps://library.ncl.res.in/content/magnesium-ligand-cooperation-breaking-o-h-and-c-h-bonds-water-and-diazoalkane