Inorganic imide

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The inorganic imide is an inorganic chemical compound containing

Contents

Organic imides have the functional groups −NH− or =NH as well.

The imides are related to the inorganic amides, containing the H2N− anions, the nitrides, containing the N3− anions and the nitridohydrides or nitride hydrides, containing both nitride N3− and hydride H− anions.

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

When covalently bound to a metal, an imide ligand produces a transition metal imido complex.

When the hydrogen of the imide group is substituted by an organic group, an organoimide results. Complexes of actinide and rare earth elements with organoimides are known. [1]

Properties

Lithium imide undergoes a phase transition at 87 °C where it goes from an ordered to a more symmetric disordered state. [2]

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. [3]

Formation

Heating lithium amide with lithium hydride yields lithium imide and hydrogen gas. This reaction takes place as released ammonia reacts with lithium hydride. [2]

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. [4]

Beryllium imide forms from beryllium amide when heated to 230 °C in a vacuum. [5]

When strontium metal is heated with ammonia at 750 °C, the dark yellow strontium imide forms. [6]

When barium vapour is heated with ammonia in an electrical discharge, the gaseous, molecular BaNH is formed. [7] Molecules ScNH, YNH, and LaNH are also known. [8] [9]

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. [10] 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

nameformulastructurespace groupunit cellreferences
Lithium imide Li2NHcubicFm3ma=5.0742 [2]
Beryllium imideBeNH [5]
Magnesium imideMgNHhexagonalP6/ma = 11.567 Å c = 3.683Å Z=12 [4]
Dilithium magnesium imideLi2Mg(NH)2 [10]
Disilicon dinitride imideSi2N2(NH) [11]
K2Si(NH)3amourphous [12]
K2Si2(NH)5amourphous [12]
K2Si3(NH)7amourphous [12]
potassium imido nitrido silicateK3Si6N5(NH)6cubicP4332a = 10.789 [11]
Calcium imideCaNHhexagonalFm3m [10]
Dilithium calcium imideLi2Ca(NH)2hexagonal [10]
Magnesium calcium diimideMgCa(NH)2cubic [13]
Lithium calcium magnesium imideLi4CaMg(NH)4 [10]
Strontium imideSrNHorthorhombicPmnaa =7.5770 b =3.92260 c =5.69652 Z=4 [6]
Tin(IV) diamide imideSn(NH2)2NH [14] [15]
Barium imideBaNHtetragonalI4/mmma=4.062 c=6.072 Z=2 [16]
Lanthanum imideLa2(NH)3rock salta=5.32 [17]
Cerium(II) imideCeNH [18]
Ytterbium(II) imideYbNHcubica=4.85 [19]
[NH4][Hg3(NH)2](NO3)3cubicP4132a = 10.304, Z = 4 [20]
Thorium(IV) dinitride imideTh2N2(NH)hexagonalP3m1a = 3.886 c = 6.185 Å [21]

Molecular

nameformulastructuresymmetryCASreferences
Boron imideB2(NH)3polymer [22]
HNObent14332-28-6
Aluminium amide imideAl(NH2)(NH)polymer [22]
Silicon dimideSi(NH)2
  • Thionitrosyl hydride
  • Azanethial
  • Azanethione
HNSbent14616-59-2 [23]
Sulfur diimide S(NH)2
Heptasulfur imide S7NH293-42-5 [24]
  • 1,2,3,4,5,7,6,8-Hexathiadiazocane
  • 1,3-Hexasulfurdiimide
  • 1,3-Diazacyclooctasulfane
H2N2S61003-75-4
  • 1,2,3,4,6,7,5,8-Hexathiadiazocane
  • 1,4-Hexasulfurdiimide
  • 1,4-Diazacyclooctasulfane
H2N2S61003-76-5
  • 1,2,3,5,6,7,4,8-Hexathiadiazocane
  • 1,5-Hexasulfurdiimide
  • 1,5-Diazacyclooctasulfane
H2N2S6
  • 1,2,3,5,7,4,6,8-Pentathiatriazocane
  • 1,3,5-Pentasulfurtriimide
  • 1,3,5-Triazacyclooctasulfane
H3N3S5638-50-6
Scandium(II) imideScNH [8]
Gallium(III) imideGa2(NH)3polymer [22]
Yttrium(II) imideYNH [8]
Barium imideBaNHlinear [3]
Lanthanum(II) imideLaNHlinearC∞v [9] [25]
Cerium(II) imideCeNHlinearC∞v [25]
Uranimine nitrideN≡U=N−H [26]
Uranimine dihydrideHN=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]

Related Research Articles

<span class="mw-page-title-main">Alkali metal</span> Group of highly reactive chemical elements

The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). Together with hydrogen they constitute group 1, which lies in the s-block of the periodic table. All alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour. This family of elements is also known as the lithium family after its leading element.

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H−), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are also called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

In chemistry, a nitride is a chemical compound of nitrogen. Nitrides can be inorganic or organic, ionic or covalent. The nitride anion, N3- ion, is very elusive but compounds of nitride are numerous, although rarely naturally occurring. Some nitrides have a found applications, such as wear-resistant coatings (e.g., titanium nitride, TiN), hard ceramic materials (e.g., silicon nitride, Si3N4), and semiconductors (e.g., gallium nitride, GaN). The development of GaN-based light emitting diodes was recognized by the 2014 Nobel Prize in Physics. Metal nitrido complexes are also common.

A solvated electron is a free electron in a solution, in which it behaves like an anion. An electron's being solvated in a solution means it is bound by the solution. The notation for a solvated electron in formulas of chemical reactions is "e−". Often, discussions of solvated electrons focus on their solutions in ammonia, which are stable for days, but solvated electrons also occur in water and many other solvents – in fact, in any solvent that mediates outer-sphere electron transfer. The solvated electron is responsible for a great deal of radiation chemistry.

In chemistry, a Zintl phase is a product of a reaction between a group 1 or group 2 and main group metal or metalloid. It is characterized by intermediate metallic/ionic bonding. Zintl phases are a subgroup of brittle, high-melting intermetallic compounds that are diamagnetic or exhibit temperature-independent paramagnetism and are poor conductors or semiconductors.

<span class="mw-page-title-main">Metal amides</span>

Metal amides (systematic name metal azanides) are a class of coordination compounds composed of a metal center with amide ligands of the form NR2−. Amido complexes of the parent amido ligand NH2− are rare compared to complexes with diorganylamido ligand, such as dimethylamido. Amide ligands have two electron pairs available for bonding.

<span class="mw-page-title-main">Lithium imide</span> Chemical compound

Lithium imide is an inorganic compound with the chemical formula Li2NH. This white solid can be formed by a reaction between lithium amide and lithium hydride.

The nitridoborates are chemical compounds of boron and nitrogen with metals. These compounds are typically produced at high temperature by reacting hexagonal boron nitride with metal nitrides or by metathesis reactions involving nitridoborates. A wide range of these compounds have been made involving lithium, alkaline earth metals and lanthanides, and their structures determined using crystallographic techniques such as X-ray crystallography. Structurally one of their interesting features is the presence of polyatomic anions of boron and nitrogen where the geometry and the B–N bond length have been interpreted in terms of π-bonding.

An oxyhydride is a mixed anion compound containing both oxide O2− and hydride ions H−. These compounds may be unexpected as the hydrogen and oxygen could be expected to react to form water. But if the metals making up the cations are electropositive enough, and the conditions are reducing enough, solid materials can be made that combine hydrogen and oxygen in the negative ion role.

In chemistry, a hydridonitride is a chemical compound that contains both hydride and nitride ions. These inorganic compounds are distinct from inorganic amides and imides as the hydrogen does not share a bond with nitrogen, and usually contain a larger proportion of metals.

The nitridosilicates are chemical compounds that have anions with nitrogen bound to silicon. Counter cations that balance the electric charge are mostly electropositive metals from the alkali metals, alkaline earths or rare earth elements. Silicon and nitrogen have similar electronegativities, so the bond between them is covalent. Nitrogen atoms are arranged around a silicon atom in a tetrahedral arrangement.

The nitridogermanates are chemical compounds containing germanium atoms bound to nitrogen. The simplest anion is GeN48−, but these are often condensed, with the elimination of nitrogen.

A chloride nitride is a mixed anion compound containing both chloride (Cl−) and nitride ions (N3−). Another name is metallochloronitrides. They are a subclass of halide nitrides or pnictide halides.

A nitridophosphate is an inorganic compound that contains nitrogen bound to a phosphorus atom, considered as replacing oxygen in a phosphate.

<span class="mw-page-title-main">Silanide</span> Anionic molecule derived from silane

A silanide is a chemical compound containing an anionic silicon(IV) centre, the parent ion being SiH−3. The hydrogen atoms can also be substituted to produce more complex derivative anions such as tris(trimethylsilyl)silanide (hypersilyl), tris(tert-butyl)silanide, tris(pentafluoroethyl)silanide, or triphenylsilanide. The simple silanide ion can also be called trihydridosilanide or silyl hydride.

A silicide hydride is a mixed anion compound that contains silicide (Si4− or clusters) and hydride (H−) anions. The hydrogen is not bound to silicon in these compounds. These can be classed as interstitial hydrides, Hydrogenated zintl phases, or Zintl phase hydrides. In the related silanides, SiH3− anions or groups occur. Where hydrogen is bonded to the silicon, this is a case of anionic hydride, and where it is bonded to a more complex anion, it would be termed polyanionic hydride.

Phosphanides are chemicals containing the [PH2]− anion. This is also known as the phosphino anion or phosphido ligand. The IUPAC name can also be dihydridophosphate(1−).

An iodide nitride is a mixed anion compound containing both iodide (I−) and nitride ions (N3−). Another name is metalloiodonitrides. They are a subclass of halide nitrides or pnictide halides. Some different kinds include ionic alkali or alkaline earth salts, small clusters where metal atoms surround a nitrogen atom, layered group 4 element 2-dimensional structures, and transition metal nitrido complexes counter-balanced with iodide ions. There is also a family with rare earth elements and nitrogen and sulfur in a cluster.

Iodide hydrides are mixed anion compounds containing hydride and iodide anions. Many iodide hydrides are cluster compounds, containing a hydrogen atom in a core, surrounded by a layer of metal atoms, encased in a shell of iodide.

Hydrogen compounds are compounds containg the element hydrogen. In these compounds, hydrogen can form in the +1 and -1 oxidation states. Hydrogen can form compounds both ionically and in covalent substances. It is a part of many organic compounds such as hydrocarbons as well as water and other organic substances. The H+ ion is often called a proton because it has one proton and no electrons, although the proton does not move freely. Brønsted–Lowry acids are capable of donating H+ ions to bases.

References

  1. ↑ 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.
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  3. 1 2 Janczyk, Alexandra; Lichtenberger, Dennis L.; Ziurys, Lucy M. (February 2006). "Competition between Metal-Amido and Metal-Imido Chemistries in the Alkaline Earth Series: An Experimental and Theoretical Study of BaNH". Journal of the American Chemical Society. 128 (4): 1109–1118. doi:10.1021/ja053473k. ISSN   0002-7863. PMID   16433526.
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  10. 1 2 3 4 5 Verbraeken, Maarten Christiaan (February 2009). Doped Alkaline Earth (nitride) Hydrides (Thesis). University of St Andrews. p. 19. hdl:10023/714.
  11. 1 2 Peters, D.; Paulus, E. F.; Jacobs, H. (1990). "Darstellung und Kristallstruktur eines Kaliumimidonitridosilicats, K3Si6N5(NH)6". Zeitschrift für anorganische und allgemeine Chemie (in German). 584 (1): 129–137. doi:10.1002/zaac.19905840112. ISSN   0044-2313.
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  14. ↑ Watney, Nicholas S. P.; Gál, Zoltán A.; Webster, Matthew D. S.; Clarke, Simon J. (2005). "The first ternary tin(ii) nitride: NaSnN". Chemical Communications (33): 4190–2. doi:10.1039/b505208d. ISSN   1359-7345. PMID   16100599.
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  17. ↑ 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.
  18. ↑ 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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  27. ↑ Li, Peng; Niu, Wenxia; Gao, Tao (2015-11-25). "Systematic analysis of structural and spectroscopic properties of neptunimine (HN=NpH2) and plutonimine (HN=PuH2)". Journal of Molecular Modeling. 21 (12): 316. doi:10.1007/s00894-015-2856-1. ISSN   0948-5023. PMID   26608606. S2CID   7587370.
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