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8.1.1 Product Subclass 1: Lithium Metal

DOI: 10.1055/sos-SD-008-00003

Dieter, R. K.Science of Synthesis, (2006843.

General Introduction

Lithium metal is soluble in liquid ammonia and amines, forming a less dense metallic bronze-colored phase in concentrated solutions.[‌1‌] Dry lithium powder reacts rapidly with air, water vapor, and nitrogen. Although moist air reacts rapidly with lithium at 25°C, the reaction with dry air or oxygen occurs at >100°C.[‌1‌] Lithium and magnesium react with nitrogen to form Li3N (ruby-red crystals) and Mg3N2, respectively. Reaction with nitrogen proceeds slowly at 25°C and rapidly at 400°C, but is inhibited by traces of oxygen.[‌1‌,‌2‌] Although lithium does not ignite upon reaction with water, large-scale lithium reactions can result in explosions during quenching. Lithium does not react with acidic terminal alkynes in the absence of transition metal halides, although lithium acetylide is formed by heating lithium metal with acetylene.[‌2‌] Lithium metal also reacts with carbon dioxide to give LiCO2. This radical anion has a half-life greater than 1 year at 25°C in a potassium bromide disk. At high metal concentrations, Li2CO2 is formed, and at high carbon dioxide concentrations (25:1) both LiC2O4 and LiCO2CO2 are formed.[‌3‌,‌4‌] Lithium metal is commercially available as chunks, ingots, powder, granules, ribbons, rods, shot, or wire packaged under argon or mineral oil and argon. It is also available as a 30wt% dispersion in mineral oil or as a free-flowing stabilized powder (LiCO2) which can be easily weighed in air.[‌5‌,‌6‌] Lithium metal with a high sodium content is available in catalyst (1wt% Na) or technical grade (<0.05wt% Na). Although the bulk metal can be activated by ultrasound irradiation, lithium in combination with an aromatic hydrocarbon can reduce many organic substrates at low temperatures.[‌7‌]

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