Synthesis and reactivity of a heteroleptic magnesium hydride on a dearomatized picolyl-based NNN-chelator†

Heteroleptic magnesium hydrides are important for their stoichiometric and catalytic reduction chemistry. Their primary nucleophilic site is typically the hydride, while the ancillary ligands commonly used are mostly spectators. Chemically non-innocent ligands in comparison are rarely applied on MgH as their reactivity can be complex. Milstein et al. have recently reported Mg-mediated alkyne hydrogenation by using their metal–ligand cooperation (MLC) concept on a dearomatized picolyl-based PNP pincer that is non-innocent with a nucleophilic nature. A ‘(PNP)MgH’ is noted as the active catalyst in hydrogenation but without structural validation. Inspired by the same, we report herein a novel NNN-chelator (^MesL) with a dearomatized picolyl moiety and its well-defined MgH. Having two prominent nucleophilic sites, the present MgH shows metal–ligand competition while reacting with certain electrophiles. It also distinguishes nonpolar alkynes and polar carbonyls by cleanly inserting itself into the former but not the latter. The nucleophilicities of the two sites are also probed by DFT methods and compared with Milstein's (PNP)MgH. Although the present system shows no MLC-type H₂ activation, the addition of a CS₂ molecule in that way is realized.