@article {49518,
	title = {Magnesium-ligand cooperation in breaking the O-H and C-H bonds of water and diazoalkane},
	journal = {Organometallics},
	volume = {44},
	year = {2025},
	month = {MAR},
	pages = {875-881},
	type = {Article},
	abstract = {<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>
},
	issn = {0276-7333},
	doi = {10.1021/acs.organomet.5c00031},
	author = {Sharma, Vishal and Dash, Soumya Ranjan and Vanka, Kumar and Gonnade, Rajesh G. and Sen, Sakya S.}
}
