Azide Complex

Transition metal azide complexes are coordination complexes containing one or more azide (N₃⁻) ligands. In addition to coordination complexes, this article summarizes homoleptic transition metal azides, which are often coordination polymers.

Structure and bonding

Azide is a pseudohalide but more nucleophilic than chloride, as reflected by the higher pKa of hydrazoic acid (4.6) vs hydrochloric acid (-5.9). As a monodentate ligand, azide binds through one of the two terminal nitrogen atoms, i.e. M-N=N=N. Azide is a "pure" sigma donor. It is classified as an X ligand in the Covalent bond classification method. In the usual electron counting method, it is a one-electron ligand.

The N₃ unit is linear or nearly so. The M-N-N angles are quite bent. Azide functions as a bridging ligand via two bonding modes. Commonly the metals share the same nitrogen ("N-diazonium" mode). Less common is the motif M-N=N=N-M, illustrated by u(N₃)(PPh₃)₂sub>2.

General synthetic methods

Traditionally, metal azide complexes are prepared by salt metathesis, e.g. the reaction of metal chlorides with sodium azide. In some cases, trimethylsilyl azide is employed as the azide source. Another popular route include acid-base reactions hydrazoic acid HN₃ and either hydrido or lewis base complexes. Still other methods rely on halide-azide exchange with trimethylsilyl azide SiMe₃N₃ with the metal fluorides as incomplete halide/azide exchange is often seen when using the chloride derivatives.

Homoleptic complexes

Many homoleptic complexes (with only one kind of ligand) are known. Coordination numbers range from 2 (e.g., u(N₃)₂sup>−) to 7 (e.g., (N₃)₇sup>−). Many homoleptic complexes are octahedral anions of the type (N₃)₆sup>n-:
*dianions for tetravalent metals V, Pt, Ti, Zr, Hf
*trianions for trivalent metals Cr, Fe, Ru, Rh, Ir
*tetraanions for the divalent Ni
For some metals, homoleptic complexes exist in two oxidation states: u(N₃)₂sup>− vs u(N₃)₄sup>− and t(N₃)₆sup>2- vs t(N₃)₄sup>2-.

Binary azide compounds can take on several structures including discrete compounds, or one- two, and three-dimensional nets, leading some to dub them as "polyazides".  Reactivity studies of azide compounds are relatively limited due to how sensitive they can be.

Group 3

Neutral unsolvated group 3 polyazide is only known for divalent europium(II) compound, Eu(N₃)₂. Attempts to react lanthanide hydroxides with HN₃ result in their basic azides, Ln(OH)(N₃)₂ or Ln(OH)₂N₃.

Group 4

Group 4 polyazides of the formula M(N₃)₄ are predicted to have linear or near linear M-N-N angles unlike their main group counterparts which are predicted to have bent M-N-N angles. This couldn’t be proved in the case of Ti(N₃)₄, owing to difficulty in crystallization. However, incorporation of large spacer counterions or N-donor adducts makes the compounds far easier to work with. In the cases of Ph₄sub>2 (N₃)₆(M=Ti, Zr, Hf), only the axial ligands exhibit near linear M-N-N angles whereas the equatorial ligands are closer to bent angles. This deviation in theory is also seen in the N-donor adducts.

The main hypothesis given for why these compounds do not have linear M-N-N angles despite theoretical calculations is that these adducts are not tetrahedral. In the homoleptic tetrahedral compounds, the nitrogen closest to the (+IV) metal center is positioned in such a way that the three valence electron pairs can donate to the vacant d orbitals on the metal and therefore the azido can act as a tridentate donor ligand in which case the expected coordination would be linear. Since the adduct compounds are not tetrahedral, the azido group can only act as a monodentate donor with two sterically active electron pairs which result in a bent M-N-N bond angles.

Group 5

The neutral binary V(IV) azide as well as V(III), V(IV), and V(V) azido ions are known. Similar to the neutral Ti(IV) azide, V(N₃)₄ is difficult to study due to high shock and temperature instability. However, (N₃)₆sup>2- paired with a large, inert counterion is relatively stable and crystalizeses as a near perfect octahedral. In contrast to V(IV), the neutral binary V(V) could not be synthesized and attempts result in the reduction of V(V) to V(IV) with the elimination of N₂ gas. Fortunately, the oxidation potentials of anions are lower than that of their parent compounds so (N₃)₆sup>− can be formed. Unlike (N₃)₆sup>2-, (N₃)₆sup>− is highly shock sensitive and distorted from octahedral symmetry with three long and three short M-N bonds in ''mer'' positions.

The neutral binary Nb(N₃)₅ and Ta(N₃)₅ also exist, and the acetonitrile adducts of these compounds contain a nearly linear azido trans to the coordinating acetonitrile. They represent the first evidence of linear M-N-N bonding. The corresponding anions b(N₃)₆sup>−, b(N₃)₇sup>2-, a(N₃)₆sup>−, and a(N₃)₇sup>2- are known and accordingly are much less shock sensitive. The structure of the hexaazido monoanions are similar to other heptaazido monoanions with bent azido ligands despite being predicted to have perfect S₆ symmetry in the gas phase for b(N₃)₆ The heptaazido dianions possess monocapped triangular-prismatic 1/4/2 structures unlike the actinide trianion (N₃)₇sup>3- which crystallizes as a monocapped octahedron or pentagonal bipyramid. Several N-donor adducts are known to exist as well. Reactions of the neutral binary NbF₅ and TaF₅ in the presence of Me₃SiN₃ with N-donors containing small bite angles such as 2,2’-bipyridine or 1,10-phenanthroline result in self ionization products of the type (N₃)₄L₂sup>+ (N₃)₆sup>− (L= N-donor) whereas N-donors containing large bite angles such as 3,3’-bipryidine or 4,4’-bipyridine produces the neutral pentaazide adducts M(N₃)₅•L (L=N-donor).

Group 6

Both Mo(N₃)₆ and W(N₃)₆ have been synthesized, and W(N₃)₆ is stable enough to grow single crystals. Contrary to group 4 and group 5 binary azido compounds, the anionic o(N₃)₇sup>− and (N₃)₇sup>− are less stable and more sensitive to handle than their neutral parent compounds.  Upon warming solutions of the heptaazido anions in either MeCN or SO₂ to room temperature, the tetraazido nitrido ions Mo(N₃)₄sup>− and W(N₃)₄sup>− are formed with elimination of N₂.

Group 7

The first Mn polyazide compound was prepared by Wöhler et al. in 1917 by reaction of MnCO₃ with HN₃ to form Mn(N₃)₂. Many divalent Mn azide salts have been synthesized. 1D chains are formed when 2,2’-bipyridine, a bidentate ligand, is used as the counter ion in the reaction between Mn(ClO₄)₂ • 6H₂O and excess NaN₃. This results in a chain with alternating EE and EO bridges which predictably gives alternating antiferromagnetic-ferromagnetic coupling. Another 2D structure is accessed via the reaction of (PPh₄)₂MnCl₂ with AgN₃ to form the Ph₄sub>2 n(N₃)₄  

The first example of a 3D azido compound was (CH₃)₄Mn(N₃)₃]. This compound has a pseudo- Perovskite (structure), perovskite structure with (CH₃)₄sup>+ ions in the cavities between the Mn centers. The azido moieties are arranged in an EE fashion, and indeed, this compound exhibits the expected antiferromagnetic behavior. The cesium analogue Cs n(N₃)₃is synthesized in a similar manner. For each 6 coordinate Mn, four of the azido linkages are EE and two are EO instead of all six being EE. This arrangement results in a honeycomb-like shape and a rare example of alternating ferro-antiferromagnetic interactions in 3D solid.

Examples of manganese azido compounds in higher oxidation states are rare. The triazide acetonitrile adduct can be prepared using the fluoride exchange route to give Mn(N₃)₃CN as a dark red shock sensitive compound. Upon addition of PPh₄N₃ the compound disproportionates into an insensitive mixture of Ph₄sub>2 n(N₃)₂and Ph₄sub>2 n(N₃)₆ The Mn(IV) salt can be prepared on its own by using Cs₂MnF₆ as the starting material to give the highly explosive Cs₂ n(N₃)₆

Group 8

Pentaazidoiron (III) ion e(N₃)₅sup>2- can be made by treating iron(III) salts with sodium azide. An iron azide reagent can be generated ''in situ''. NaN₃ and iron (III) sulfate Fe₂(SO₄)₃ are combined in methanol and added to an organoborane followed by slow addition of 30% hydrogen peroxide, presumably forming Fe(N₃)₃. When combined with alkenes, the equivalent of hydrogen azide add in an anti-Markovnikov fashion.

-Bu₄Nsub>3 u(N₃)₆is prepared by treating K₂ u^IVCl₆with NaN₃. N₂ gas is liberated in this reaction, which involves reduction of Ru(IV) to Ru(III).

Group 9

Tetraazido cobalt(II) compounds have been isolated as both the tetraphenylphosphonium and tetraphenylarsonium salts from solutions of cobalt sulfate with a 15 time sexcess of NaN₃ to yield h₄Psub>2 o(N₃)₄and h₄Assub>2 o(N₃)₄respectively. The autooxidation of solutions of   o(N₃)₄sup>2- can be used as a colorimetric spot test for the presence of sulfite ions.

Tetrabutylammonium salts of rhodium(III) and iridium(III) azides are known and are prepared by reacting a large excess of NaN₃ in an aqueous solution with the corresponding Na₃ Cl₆• 12H₂O metal chloride salt to form -Bu₄Nsub>3 h(N₃)₆and -Bu₄Nsub>3 r(N₃)₆

Group 10

The binary nickel azide Ni(N₃)₂ has been prepared by distilling HN₃ onto nickel carbonate. Samples of Ni(N₃)₂ decompose upon heating .

d(N₃)₄sup>2- anions are square planar and the degree of interaction between the anion and its corresponding cation can be determined by the amount of deviation in the torsion angles from the ideal geometry. Various platinates t(N₃)₄sup>2- and t(N₃)₆sup>4- are known and are prepared from Pt chloride salts with NaN₃. Pt(II) salts tend to be far less stable than the Pt(IV) versions, and they either decompose fairly rapidly upon standing or explode. Their sensitivity in part has been explained by poor crystal packing.

Group 11

Both copper(I) and copper(II) azides are known. The binary copper(I) azide, CuN₃, which is white, is a one-dimensional polymer. Molecular Copper (II) azides include salts of u(N₃)₄sup>2- and u(N₃)₆sup>2-. _n forms 1D chains wherein octahedral Cu(II) centers are linked by both EE and EO bridging azides. All copper azides are explosive but their sensitivities vary widely from the parent azides CuN₃ and Cu(N₃)₂ which are extremely sensitive to the ions paired with large countercations that are practically insensitive.

Silver (I) azide is a well known explosive compound and has been demonstrated to form a 2D coordination polymer with square planar Ag⁺ ions surrounded by azido ligands in an EE fashion. Slow ramping of temperature from 150 °C to 251 °C results in melting and slow decomposition but rapid heating to 300 °C results in an explosion.

Gold(III) azide is known as the tetraethylammonium salt t₄NAu(N₃)₄] and also adopts a square planar structure. However unlike the silver azide, the gold azide is not stable at room temperature and will decompose after a few days and its metal azide bonds have significant covalent character.

Group 12

While Zinc azide, Zn(N₃)₂ has been known since the late 1890s, solvent free Zn(N₃)₂ was isolated for the first time in 2016 from a dry ethereal solution of HN₃ and Et₂Zn in ''n''-hexane. Zn(N₃)₂ crystallizes in three different polymorphs α-Zn(N₃)₂ and the labile β-Zn(N₃)₂ and γ-Zn(N₃)₂ forms.

The first mercury (I) azide was realized by Curtius in 1890 by combining aqueous mercury(I) salts with alkali metal azides and by combining HN₃ with elemental mercury to produce Hg₂(N₃)₂. Both mercury (I) and mercury(II) azides can be easily prepared by mixing the respective mercury nitrates with sodium azide in aqueous solution at roomtemperature. The mercury (II) azide Hg(N₃)₂ exists in two polymorphs α-Hg(N₃)₂ and β-Hg(N₃)_2. The β form is very labile and quickly turns into the α polymorphs at room temperature. However, the β polymorph can prepared in analogy to β-Pb(N₃)₂ by slow diffusion of aqueous NaN₃ into a solution of Hg(NO₃)₂ separated by a layer of aqueous NaNO₃, but crystals nearly always explode during formation leading to a mixture of α and β polymorphs.

Binary cadmium azide Cd(N₃)₂ can be prepared from CdCO₃ and aqueous HN₃. However, it is structural unrelated to the mercury or zinc anaolgues and is based on repeat units of Cd₂(N₃)₁₀ double octahedrals.

Mixed ligand complexes

Azide forms myriad mixed ligand complexes. Examples include Zn(N₃)₂(NH₃)₂ and (C₅H₅)₂Ti(N₃)₂.

Reactions

A characteristic reaction of azide complexes and compounds) is degradation via loss of nitrogen gas. The stoichiometry for a diazide compound is:
:
The process often occurs explosively.

Azide ligands are react with nitrosonium to give nitrous oxide. This reaction is used to generate coordinatively unsaturated complexes.
: o(NH₃)₅N₃sup>2+ + NO⁺ + H₂O → o(NH₃)₅(H₂O)sup>3+ + N₂O + N₂

This approach was used to prepare the previously elusive dicationic complex pentamminecobalt(III) perchlorate, .

See also

* Main group azido compounds

References

{{Coordination complexes

Ligands
Azides