Inorganic imide

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The inorganic imides are compounds containing an ion composed of nitrogen bonded to hydrogen with formula HN2−. Organic imides have the NH group, and two single or one double covalent bond to other atoms. The imides are related to the (H2N−), the nitrides (N3−) and the nitridohydrides (N3−•H−).

In addition to solid state imides, molecular imides are also known in dilute gases, where their spectrum can be studied.

Imide can be a ligand, with a double bond to a metal such as molybdenum (eg Mo=NH). As a ligand it is called imido. The imido ligand is part of a nitrogen fixation cycle: Mo•N2 → Mo-N=N− → Mo-N=NH (diazenido) → Mo-N=NH2+ → Mo=N-NH2 (hydrazido) → Mo=N-NH3+ (hydrazidium) → Mo≡N (nitrido) + NH3 → Mo≡NH+ → Mo=NH (imido) → Mo=NH2+ → Mo-NH2 (amido) → Mo-NH3+ → Mo•NH3 (ammine); with the oxidation state of molydenum varying to accommodate the number bonds from nitrogen.[1]

When the hydrogen of the imide group is substituted by an organic group, an results. Complexes of actinide and rare earth elements with organoimides are known.[2]

Properties[]

Lithium imide undergoes a phase transition at 87° C where it goes from an ordered to a more symmetric disordered state.[3]

Structure[]

Many imides have a cubic rock salt structure, with the metal and nitrogen occupying the main positions. The position of the hydrogen atom is hard to determine, but is disordered.

Many of the heavy metal simple imide molecules are linear. This is due to the filled 2p orbital of nitrogen donating electrons to an empty d orbital on the metal.[4]

Formation[]

Heating lithium amide with lithium hydride yields lithium imide and hydrogen gas. This reaction takes place as released ammonia reacts with lithium hydride.[3]

Heating magnesium amide to about 400°C yields magnesium imide with the loss of ammonia. Magnesium imide itself decomposes if heated between 455 and 490°C.[5]

Beryllium imide forms from beryllium amide when heated to 230°C in a vacuum.[6]

When strontium metal is heated with ammonia at 750°C, the dark yellow strontium imide forms.[7]

When barium vapour is heated with ammonia in an electrical discharge, the gaseous, molecular BaNH is formed.[8] Molecules ScNH, YNH, and LaNH are also known.[9][10]

Hydrogen storage[]

Inorganic imides are of interest because they can reversibly store hydrogen, which may be important for the hydrogen economy. For example calcium imide can store 2.1% mass of hydrogen. Li2Ca(NH)2 reversibly stores hydrogen and release it at temperatures between 140 and 206°C. It can reversibly hold 2.3% hydrogen.[11] When hydrogen is added to the imide, amides and hydrides are produced. When imides are heated, they can yield hydridonitrides or nitrides, but these may not easily reabsorb hydrogen.

List[]

Ionic[]

name formula structure space group unit cell references
Lithium imide Li2NH cubic Fm3m a=5.0742 [3]
Beryllium imide BeNH [6]
Magnesium imide MgNH hexagonal P6/m a = 11.567 Å c = 3.683Å Z=12 [5]
Lithium magnesium imide Li2Mg(NH)2 [11]
Si2N2(NH) [12]
K2Si(NH)3 amourphous [13]
K2Si2(NH)5 amourphous [13]
K2Si3(NH)7 amourphous [13]
potassium imido nitrido silicate K3Si6N5(NH)6 cubic P4332 a = 10.789 [12]
Calcium imide CaNH hexagonal Fm3m [11]
Lithium calcium imide Li2Ca(NH)2 hexagonal [11]
Magnesium calcium diimide MgCa(NH)2 cubic [14]
Lithium calcium magnesium imide Li4CaMg(NH)4 [11]
Strontium imide SrNH orthorhombic Pmna a =7.5770 b =3.92260 c =5.69652 Z=4 [7]
Tin amide imide Sn(NH2)2NH [15][16]
Barium imide BaNH tetragonal I4/mmm a=4.062 c=6.072 Z=2 [17]
Lanthanum imide La2(NH)3 rock salt a=5.32 [18]
Cerium imide CeNH [19]
Ytterbium imide YbNH cubic a=4.85 [20]
Thorium nitride imide Th2N2(NH) hexagonal P3m1 a = 3.886 c = 6.185 Å [21]

Molecular[]

name formula structure symmetry CAS references
B2(NH)3 polymer [22]
Nitroxyl HNO bent 14332-28-6
Al(NH2)(NH) polymer [22]
silicon dimide Si(NH)2
thionitrosyl hydride HNS bent 14616-59-2 [23]
sulfur diimide S(NH)2
Heptasulfur imide S7NH 293-42-5 [24]
1,2,3,4,5,7,6,8-Hexathiadiazocane

1,3-Hexasulfurdiimide

H2N2S6 1003-75-4
1,2,3,4,6,7,5,8-Hexathiadiazocane

1,4-Hexasulfurdiimide

H2N2S6 1003-76-5
1,2,3,5,6,7,4,8-Hexathiadiazocane

1,5-Hexasulfurdiimide

H2N2S6
1,2,3,5,7,4,6,8-Pentathiatriazocane H3N3S5 638-50-6
ScNH [9]
Ga2(NH)3 polymer [22]
YNH [9]
BaNH linear [4]
LaNH linear C∞v [10][25]
CeNH linear C∞v [25]
Uranimine nitride N≡U═N−H [26]
Uranimine dihydride HN═UH2 [26]

Molecular imines of other actinides called neptunimine and plutonimine have been postulated to exist in the gas phase or noble gas matrix.[27]

References[]

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  2. ^ Schädle, Dorothea; Anwander, Reiner (2019). "Rare-earth metal and actinide organoimide chemistry". Chemical Society Reviews. 48 (24): 5752–5805. doi:10.1039/c8cs00932e. PMID 31720564. S2CID 207938163.
  3. ^ a b c Lowton, Rebecca L. (1999). Structural and thermogravimetric studies of alkali metal amides and imides (http://purl.org/dc/dcmitype/Text thesis). Oxford University, UK. {{cite thesis}}: External link in |degree= (help)
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  17. ^ Wegner, B.; Essmann, R.; Jacobs, H.; Fischer, P. (December 1990). "Synthesis of barium imide from the elements and orientational disorder of anions in BaND studied by neutron diffraction from 8 to 294 K". Journal of the Less Common Metals. 167 (1): 81–90. doi:10.1016/0022-5088(90)90291-Q.
  18. ^ Jacobs, H; Gieger, B; Hadenfeldt, C (March 1979). "Über das system kalium/lanthan/ammoniak". Journal of the Less Common Metals (in German). 64 (1): 91–99. doi:10.1016/0022-5088(79)90136-X.
  19. ^ Imamura, Hayao; Kawasoe, Masahiro; Imayoshi, Kyouya; Sakata, Yoshihisa (2015). "Preparation and Some Properties of Nanostructural Rare Earth Nitrides by Using the Reaction of Hydrides with Ammonia". International Journal of Theoretical and Applied Nanotechnology. 3: 1–8. doi:10.11159/ijtan.2015.001.
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  22. ^ a b c Janik, Jerzy F.; Wells, Richard L. (January 1996). "Gallium Imide, {Ga(NH) 3/2 } n , a New Polymeric Precursor for Gallium Nitride Powders". Chemistry of Materials. 8 (12): 2708–2711. doi:10.1021/cm960419h. ISSN 0897-4756.
  23. ^ Nguyen, Minh Tho; Vanquickenborne, L.G.; Plisnier, Michel; Flammang, Robert (January 1993). "A mass spectrometric and ab initio molecular orbital characterization of thionitrosyl hydride (H-N=S)". Molecular Physics. 78 (1): 111–119. Bibcode:1993MolPh..78..111N. doi:10.1080/00268979300100111. ISSN 0026-8976.
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