Indium trihydride

Indium trihydride
Names
Systematic IUPAC name
Indigane[1] (substitutive)
Trihydridoindium[1] (additive)
Other names
Indium(III) hydride
Indium trihydride
Identifiers
3D model (Jmol) Interactive image
ChEBI CHEBI:30429 YesY
ChemSpider 22435 YesY
163932
PubChem 24000
Properties
InH
3
Molar mass 117.842 g mol−1
Structure
Trigonal planar
Dihedral
Related compounds
Related metallanes
 Aluminium hydride

Borane
Hydrogen iodide
Hydrogen telluride
Rubidium hydride
Stannane
Stibine

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Indium trihydride is an inorganic compound with the chemical formula (InH
3)n (also written as ([InH
3])n or InH
3). It is a covalent network solid, and as such, it is insoluble in all solvents. Moreover, it is unstable at standard temperature and pressure.[2] It is a group 13 hydride.

Nomenclature

The systematic name indium trihydride, a valid IUPAC name, is constructed according to the compositional nomenclature. Indium trihydride is also used to refer to the related molecular compound indigane and its oligomers. Care should be taken to avoid confusing the two compounds.

Chemical properties

For solid InH3 a three-dimensional network polymeric structure, where In atoms are connected by In-H-In bridging bonds, is suggested to account for the growth of broad infrared bands when samples of InH3 and InD3 produced on a solid hydrogen matrix are warmed.[2] Such a structure is known for solid AlH3.[3] When heated above −90 °C (−130 °F), indium trihydride decomposes to produce indium–hydrogen alloy and elemental hydrogen. As of 2013, the only known method of synthesising indium trihydride, is the autopolymerisation of indigane below −90 °C (−130 °F).

Indigane

Indigane (also systematically named trihydridoindium), also called indane, is the monomer with the chemical formula InH
3 (also written [InH
3]). It is a colourless gas that cannot persist undiluted. Indigane is the simplest of the indiganes. Unsolvated indigane will spontaneously autopolymerise, first to oligomers, and finally indium trihydride.

It has been observed in matrix isolation.[4][5] Gas phase stability has been predicted [6] The infrared spectrum was obtained in the gas phase by laser ablation of indium in presence of hydrogen gas [2] Several indium hydride complexes have been reported.[7] Examples of complexes with two hydride ligands replaced by other ligands are K3[K(Me2SiO)7][HIn(Me3CCH2)3]4 [8] and HIn(2-Me2NCH2-C6H4)2.

Lewis Acidity

A number of indium hydride adducts are known. These include 1:1 adducts with four coordinate indium and 2:1 adducts with five coordinate indium. Typically the 1:1 amine complexes are made by the reaction of indium tribromide with lithium hydride to form LiInH4 in solution which then is reacted with a trialkylammonium chloride. The 2:1 complex with tricyclohexylphosphine (PCy3) may be produced by reacting the 1:1 trimethylammonium complex with PCy3. These adducts are not all stable, for example the trimethylammonium complex is stable only below −30 °C or in dilute solution. The 1:1 and 2:1 complexes with of PCy3 have been characterised crystallographically and the average In-H bond length was found to be 168 pm, which is considerably longer than the corresponding Al-H and Ga-H bonds.[9] Indium hydride is also known to form adducts with carbenes.[10]

The indium atom in indiganes such as indigane can accept an electron-pair donating ligand into the molecule by adduction:[11]

[InH
3] + L → [InH
3L]

Because of this acceptance of the electron-pair donating ligand (L), indigane has Lewis-acidic character. Indigane can accept one electron-pair from a ligand, as in the case of the tetrahydridoindate(1−) anion (InH−
4).[12]

References

  1. 1 2 "Indigane (CHEBI:30429)". Chemical Entities of Biological Interest (ChEBI). UK: Europen Bioinformatics Institute.
  2. 1 2 3 Andrews, L.; Wang, X. (2004). "Infrared Spectra of Indium Hydrides in Solid Hydrogen and of Solid Indane". Angewandte Chemie International Edition. 43: 1706–1709. doi:10.1002/anie.200353216.
  3. ↑ Turley, J. W.; Rinn, H. W. (1969). "The Crystal Structure of Aluminum Hydride". Inorganic Chemistry. 8 (1): 18–22. doi:10.1021/ic50071a005.
  4. ↑ Aluminium, gallium and indium trihydrides. an IR matrix isolation and ab initio study Chemical Physics, Volume 185, Issue 1, 1 July 1994, Pages 25-37 P. Pullumbi, Y. Bouteiller, L. Manceron, C. Mijoule
  5. ↑ Hydrides of the Main-Group Metals: New Variations on an Old Theme Simon Aldridge , Anthony J. Downs Chem. Rev., 2001, 101 (11), pp 3305–3366 doi:10.1021/cr960151d
  6. ↑ Are the Compounds InH3 and TlH3 Stable Gas Phase or Solid State Species? Patricia Hunt and Peter Schwerdtfeger Inorg. Chem., 1996, 35 (7), pp 2085–2088 doi:10.1021/ic950411u
  7. ↑ Synthesis, crystal and molecular structure of the first indium trihydride complex, [InH3{Cupper bond 1 startN(Pri)C2Me2Nupper bond 1 end(Pri)}] David E. Hibbs, Michael B. Hursthouse, Michael B. Hursthouse, Cameron Jones and Neil A. Smithies Chem. Commun., 1998, 869-870 doi:10.1039/A801118D
  8. ↑ Silicone grease as a precursor to a pseudo crown ether ligand: crystal structure of [K+]3[K(Me2SiO)7+][InH(CH2CMe3)3–]4 Melvyn Rowen Churchill, Charles H. Lake, Sun-Hua L. Chao and O. T. Beachley J. Chem. Soc., Chem. Commun., 1993, 1577-1578 doi:10.1039/C39930001577
  9. ↑ Jones, Cameron (2001). "The stabilisation and reactivity of indium trihydride complexes". Chemical Communications (22): 2293–2298. doi:10.1039/b107285b. ISSN 1359-7345.
  10. ↑ Preparation, Characterization, and Reactivity of the Stable Indium Trihydride Complex [InH3{CN(Mes)C2H2N(Mes)}] Colin D. Abernethy, Marcus L. Cole, and Cameron Jones Organometallics, 2000, 19 (23), pp 4852–4857 doi:10.1021/om0004951
  11. ↑ Wang, Xuefeng; Andrews, Lester (20 May 2004). "Infrared Spectra of Indium Hydrides in Solid Hydrogen and Neon". The Journal of Physical Chemistry A. ACS Publications. 108 (20): 4440–4448. doi:10.1021/jp037942l.
  12. ↑ Derrah, Eric J.; Sircoglou, Marie; Mercy, Maxime; Ladeira, Sonia; Bouhadir, Ghenwa; Miqueu, Karinne; Maron, Laurent; Bourissou, Didier (28 February 2011). "Original Transition Metal→Indium Interactions upon Coordination of a Triphosphine−Indane". Organometallics. 30 (4): 657–660. doi:10.1021/om1011769.
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