Methyllithium (MeLi) is the parent archetypical organolithium complex and its monomeric form is vital for understanding the ubiquitous organolithium-mediated reactions. However, despite being pursued for decades, to the best of...

In this work, a rare monomeric organolithium complex was reported, stabilised by a neutral tetradentate amine ligand. Its structure and decomposition/reactivity were studied.

Organosodium chemistry is underdeveloped compared with organolithium chemistry, and all the reported organosodium complexes exhibit similar, if not identical, reactivity patterns to their lithium counterparts. Herein, we report a rare organosodium monomeric complex, namely, [Na(CH 2 SiMe 3 )(Me 6 Tren)] (1-Na) (Me 6 Tren: tris[2-(dimethylamino)ethyl]amine) stabilized by a tetra-dentate neutral amine ligand Me 6 Tren. Employing organo-carbonyl substrates (ketones, aldehydes, amides, ester), we demonstrated that 1-Na features distinct reactivity patterns compared with its lithium counterpart, [Li(CH 2 SiMe 3 )(Me 6 Tren)] (1-Li). Based on this knowledge, we further developed a ligand-catalysis strategy to conduct ketone/aldehyde methylenations, using [NaCH 2 SiMe 3 ] ∞ as the CH 2 feedstock, replacing the widely used but hazardous/expensive C�O methylenation methods, such as Wittig, Tebbe, Julia/Julia-Kocienśki, Peterson, and so on.

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