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Metal bis(trimethylsilyl)amides (often abbreviated as metal silylamides) are coordination complexes composed of a cationic metal with anionic bis(trimethylsilyl)amide ligands and are part of a broader category of metal amides.
Contents
- General methods of preparation
- Group 1 complexes
- Group 2 complexes
- p Block complexes
- d Block complexes
- f Block complexes
- Safety
- References
Due to the bulky hydrocarbon backbone metal bis(trimethylsilyl)amide complexes have low lattice energies and are lipophilic . For this reason, they are soluble in a range of nonpolar organic solvents, in contrast to simple metal halides, which only dissolve in reactive solvents. These steric bulky complexes are molecular, consisting of mono-, di-, and tetramers. Having a built-in base, these compounds conveniently react with even weakly protic reagents. The class of ligands and pioneering studies on their coordination compounds were described by Bürger and Wannagat.
The ligands are often denoted hmds (e.g. M(N(SiMe3)2)3 = M(hmds)3) in reference to the hexamethyldisilazide from which they are prepared.
General methods of preparation
Apart from group 1 and 2 complexes, a general method for preparing metal bis(trimethylsilyl)amides entails reactions of anhydrous metal chloride with an alkali metal bis(trimethylsilyl)amides via a salt metathesis reaction:
MCln + n Na(hmds) → M(hmds)n + n NaClAlkali metal chloride formed as a by-product typically precipitates as a solid, allowing for its removal by filtration. The remaining metal bis(trimethylsilyl)amide is then often purified by distillation or sublimation.
Group 1 complexes
Lithium, sodium, and potassium bis(trimethylsilyl)amides are commercially available. When free of solvent, the lithium and sodium complexes are trimeric, and the potassium complex is dimeric in solid state. The lithium reagent may be prepared from n-butyllithium and bis(trimethylsilyl)amine:
nBuLi + HN(SiMe3)2 → Li(hmds) + butaneThe direct reaction of these molten metals with bis(trimethylsilyl)amine at high temperature has also been described:
M + HN(SiMe3)2 → MN(SiMe3)2 + 1/2 H2Alkali metal silylamides are soluble in a range of organic solvents, where they exist as aggregates, and are commonly used in organic chemistry as strong sterically hindered bases. They are also extensively used as precursors for the synthesis other bis(trimethylsilyl)amide complexes (see below).
Group 2 complexes
The calcium and barium complexes may be prepared via the general method, by treating calcium iodide or barium chloride with potassium or sodium bis(trimethylsilyl)amide. However, this method can result in potassium contamination. An improved synthesis involving the reaction of benzylpotassium with calcium iodide, followed by reaction with bis(trimethylsilyl)amine results in potassium-free material:
2 BzK + CaI2 + THF → Bz2Ca(thf) + KI Bz2Ca(thf) + 2 HN(SiMe3)2 → Ca(hmds)2 + 2 C6H5CH3 + THFMagnesium silylamides can be prepared from dibutylmagnesium; which is commercially available as a mixture of n-Bu and s-Bu isomers. It deprotonates the free amine to yield the magnesium bis(trimethylsilyl)amide, itself commercially available.
Bu2Mg + 2 HN(SiMe3)2 → Mg(hmds)2 + 2 butaneIn contrast to group 1 metals, the amine N-H in bis(trimethylsilyl)amine is not acidic enough to react with the group 2 metals, however complexes may be prepared via a reaction of tin(II) bis(trimethylsilyl)amide with the appropriate metal:
M + 2 HN(SiMe3)2 –/→ M(hmds)2 + H2 (M = Mg, Ca, Sr, Ba) M + Sn(hmds)2 → M(hmds)2 + SnLong reaction times are required for this synthesis and when performed in the presence of coordinating solvents, such as dimethoxyethane, adducts are formed. Hence non-coordinating solvents such as benzene or toluene must be used to obtain the free complexes.
p-Block complexes
Tin(II) bis(trimethylsilyl)amide is prepared from anhydrous tin(II) chloride and is commercially available. It is used to prepare other metal bis(trimethylsilylamide)s via transmetallation. The group 13 and bismuth(III) bis(trimethylsilyl)amides are prepared in the same manner; the aluminium complex may also be prepared by treating strongly basic lithium aluminium hydride with the parent amine:
LiAlH4 + 4 HN(SiMe3)2 → Li(hmds) + Al(hmds)3 + 4 H2d-Block complexes
In line with the general method, bis(trimethylsilyl)amides of transition metals are prepared by a reaction between the metal halides (typically chlorides) and sodium bis(trimethylsilyl)amide, some variation does exist however, for instance the synthesis of blue Ti(N(SiMe3)2)3 using the soluble precursor TiCl3(Et3N)3. The melting and boiling points of the complexes decrease across the series, with Group 12 metals being sufficiently volatile to allow purification by distillation.
Iron complexes are notable for having been isolated in both the ferrous (II) and ferric (III) oxidation states. Fe[N(SiMe3)2]3 can be prepared by treating iron trichloride with lithium bis(trimethylsilyl)amide and is paramagnetic as the high spin iron(III) contains 5 unpaired electrons.
FeCl3 + 3LiN(SiMe3)2 → Fe[N(SiMe3)2]3 + 3LiClSimilarly, the two coordinate Fe[N(SiMe3)2]2 complex is prepared by treating iron dichloride with lithium bis(trimethylsilyl)amide:
FeCl2 + 2LiN(SiMe3)2 → Fe[N(SiMe3)2]2 + 2LiClThe dark green Fe[N(SiMe3)2]2 complex exists in two forms depending on its physical state. At room temperature the compound is a monomeric liquid with two-coordinate Fe centers possessing S4 symmetry, in the solid state it forms a dimer with trigonal planar iron centers and bridging amido groups. The low coordination number of the iron complex is largely due to the steric effects of the bulky bis(trimethylsilyl)amide, however the complex will bind THF to give the adduct, {(THF)Fe[N(SiMe3)2]2}. Similar behavior can be seen in Mn(hmds)2 and Co(hmds)2, which are monomeric in the gas phase and dimeric in the crystalline phase. Group 11 complexes are especially prone to oligomerization, forming tetramers in the solid phase.
f-Block complexes
Lanthanide triflates can be convenient anhydrous precursors to many bis(trimethylsilyl)amides:
Ln(OTf)3 + 3 M(hmds) → Ln(hmds)3 + 3 MOTf (M = Li, Na, K; Ln = La, Nd, Sm, Er)However it is more common to see the preparation of lanthanide bis(trimethylsilyl)amides from anhydrous lanthanide chlorides, as these are cheaper. The reaction is performed in THF and requires a period at reflux. Once formed, the product is separated from LiCl by exchanging the solvent for toluene, in which Ln(hmds)3 is soluble but LiCl is not.
Ln(Cl)3 + 3 HMDS + 3 nBuLi → Ln(hmds)3 + 3 LiCl + 3 butane (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Yb, and Lu)Silylamides are important as starting materials in lanthanide chemistry, as lanthanide chlorides have either poor solubility or poor stability in common solvents. As a result of this nearly all lanthanide silylamides are commercially available.
There has also been some success in the synthesis and characterization of actinide bis(trimethylsilyl)amides. A convenient synthetic route uses the THF-adducts of the iodide salts AnI3(THF)4 as starting materials.
Safety
Metal bis(trimethylsilyl)amides are strong bases. They are corrosive, and are incompatible with many chlorinated solvents. These compounds react vigorously with water, and should be manipulated with air-free technique.