Lithium bis(trimethylsilyl)amide


Lithium bisamide is a lithiated organosilicon compound with the formula LiN2. It is commonly abbreviated as LiHMDS and is primarily used as a strong non-nucleophilic base and as a ligand. Like many lithium reagents, it has a tendency to aggregate and will form a cyclic trimer in the absence of coordinating species.

Preparation

LiHMDS is commercially available, but it can also be prepared by the deprotonation of bisamine with n-butyllithium. This reaction can be performed in situ.
Once formed, the compound can be purified by sublimation or distillation.

Reactions and applications

As a base

LiHMDS is often used in organic chemistry as a strong non-nucleophilic base. Its conjugate acid has a pKa of ~26, making it is less basic than other lithium bases, such as LDA, but it is more sterically hindered and hence less nucleophilic. It can be used to form various organolithium compounds, including acetylides or lithium enolates.
As such, it finds use in a range of coupling reactions, particularly carbon-carbon bond forming reactions such as the Fráter–Seebach alkylation and mixed Claisen condensations.
An alternative synthesis of tetrasulfur tetranitride entails the use of 2S as a precursor with pre-formed S-N bonds. 2S is prepared by the reaction of lithium bisamide and sulfur dichloride.
The 2S reacts with the combination of SCl2 and sulfuryl chloride to form S4N4, trimethylsilyl chloride, and sulfur dioxide:

As a ligand

LiHMDS can react with a wide range of metal halides, by a salt metathesis reaction, to give metal bisamides.
Metal bisamide complexes are lipophilic due to the ligand and hence are soluble in a range of nonpolar organic solvents, this often makes them more reactive than the corresponding metal halides, which can be difficult to solubilise. The steric bulk of the ligands causes their complexes to be discrete and monomeric; further increasing their reactivity. Having a built-in base, these compounds conveniently react with protic ligand precursors to give other metal complexes and hence are important precursors to more complex coordination compounds.

Niche uses

LiHMDS is volatile and has been discussed for use for atomic layer deposition of lithium compounds.

Structure

Like many organolithium reagents, lithium bisamide can form aggregates in solution. The extent of aggregation depends on the solvent. In coordinating solvents, such as ethers and amines, the monomer and dimer are prevalent. In the monomeric and dimeric state, one or two solvent molecules bind to lithium centers. With ammonia as donor base lithium bisamide forms a trisolvated monomer that is stabilized by intermolecular hydrogen bonds. In noncoordinating solvents, such as aromatics or pentane, the complex oligomers predominate, including the trimer. In the solid state structure is trimeric.