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]

Imides in coordination chemistry

In coordination chemistry transition metal imido complexes feature the NR2- ligand. They are similar to oxo ligands in some respects. In some the M-N-C angle is 180º but often the angle is decidedly bent. The parent imide (NH2-) is an intermediate in nitrogen fixation by synthetic catalysts. [4]

Structure of a representative imido complex (py = pyridine, CMe3 = tert-butyl) TiImide.png
Structure of a representative imido complex (py = pyridine, CMe3 = tert-butyl)

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. [6]

Beryllium imide forms from beryllium amide when heated to 230 °C in a vacuum. [7]

When strontium metal is heated with ammonia at 750 °C, the dark yellow strontium imide forms. [8]

When barium vapour is heated with ammonia in an electrical discharge, the gaseous, molecular BaNH is formed. [9] Molecules ScNH, YNH, and LaNH are also known. [10] [11]

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. [12] 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 [7]
Magnesium imideMgNHhexagonalP6/ma = 11.567 Å c = 3.683Å Z=12 [6]
Dilithium magnesium imideLi2Mg(NH)2 [12]
Disilicon dinitride imideSi2N2(NH) [13]
K2Si(NH)3amourphous [14]
K2Si2(NH)5amourphous [14]
K2Si3(NH)7amourphous [14]
potassium imido nitrido silicateK3Si6N5(NH)6cubicP4332a = 10.789 [13]
Calcium imideCaNHhexagonalFm3m [12]
Dilithium calcium imideLi2Ca(NH)2hexagonal [12]
Magnesium calcium diimideMgCa(NH)2cubic [15]
Lithium calcium magnesium imideLi4CaMg(NH)4 [12]
Strontium imideSrNHorthorhombicPmnaa =7.5770 b =3.92260 c =5.69652 Z=4 [8]
Tin(IV) diamide imideSn(NH2)2NH [16] [17]
Barium imideBaNHtetragonalI4/mmma=4.062 c=6.072 Z=2 [18]
Lanthanum imideLa2(NH)3rock salta=5.32 [19]
Cerium(II) imideCeNH [20]
Ytterbium(II) imideYbNHcubica=4.85 [21]
[NH4][Hg3(NH)2](NO3)3cubicP4132a = 10.304, Z = 4 [22]
Thorium(IV) dinitride imideTh2N2(NH)hexagonalP3m1a = 3.886 c = 6.185 Å [23]

Molecular

nameformulastructuresymmetryCASreferences
Boron imideB2(NH)3polymer [24]
HNObent14332-28-6
Aluminium amide imideAl(NH2)(NH)polymer [24]
Silicon dimideSi(NH)2
  • Thionitrosyl hydride
  • Azanethial
  • Azanethione
HNSbent14616-59-2 [25]
Sulfur diimide S(NH)2
Heptasulfur imide S7NH293-42-5 [26]
  • 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 [10]
Gallium(III) imideGa2(NH)3polymer [24]
Yttrium(II) imideYNH [10]
Barium imideBaNHlinear [3]
Lanthanum(II) imideLaNHlinearC∞v [11] [27]
Cerium(II) imideCeNHlinearC∞v [27]
Uranimine nitrideN≡U=N−H [28]
Uranimine dihydrideHN=UH2 [28]

Molecular imines of other actinides called neptunimine and plutonimine have been postulated to exist in the gas phase or noble gas matrix. [29]

Related Research Articles

<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.

In chemistry, an acetylide is a compound that can be viewed as the result of replacing one or both hydrogen atoms of acetylene (ethyne) HC≡CH by metallic or other cations. The term is also used, more loosely, for any compound obtained in the same way from an acetylene derivative RC≡CH, where R is some organic side chain.

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

Lithium nitride is an inorganic compound with the chemical formula Li3N. It is the only stable alkali metal nitride. It is a reddish-pink solid with a high melting point.

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

Lithium amide or lithium azanide is an inorganic compound with the chemical formula LiNH2. It is a white solid with a tetragonal crystal structure. Lithium amide can be made by treating lithium metal with liquid ammonia:

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

Lithium carbide, Li2C2, often known as dilithium acetylide, is a chemical compound of lithium and carbon, an acetylide. It is an intermediate compound produced during radiocarbon dating procedures. Li2C2 is one of an extensive range of lithium-carbon compounds which include the lithium-rich Li4C, Li6C2, Li8C3, Li6C3, Li4C3, Li4C5, and the graphite intercalation compounds LiC6, LiC12, and LiC18.

<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.

<span class="mw-page-title-main">Nitrogen pentahydride</span> Chemical compound

Nitrogen pentahydride, also known as ammonium hydride is a hypothetical compound with the chemical formula NH5. There are two theoretical structures of nitrogen pentahydride. One structure is trigonal bipyramidal molecular geometry type NH5 molecule. Its nitrogen atom and hydrogen atoms are covalently bounded, and its symmetry group is D3h. Another predicted structure of nitrogen pentahydride is an ionic compound, composed of an ammonium ion and a hydride ion (NH4+H−). Until now, no one has synthesized this substance, or proved its existence, and related experiments have not directly observed nitrogen pentahydride. It is only speculated that it may be a reactive intermediate based on reaction products. Theoretical calculations show this molecule is thermodynamically unstable. The reason might be similar to the instability of nitrogen pentafluoride, so the possibility of its existence is low. However, nitrogen pentahydride might exist in special conditions or high pressure. Nitrogen pentahydride was considered for use as a solid rocket fuel for research in 1966.

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.

Hydrogen compounds are compounds containing 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

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  29. ↑ 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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