Iron(II) hydride

Iron(II) hydride
Names
Systematic IUPAC name
Dihydridoiron(4•)
Identifiers
33485-98-2
3D model (Jmol) Interactive image
ChemSpider 124509
PubChem 141155
Properties
FeH24•
Molar mass 57.861 g mol−1
Related compounds
Related compounds
 iron hydrides, FeH, FeH3
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Iron(II) hydride (systematically named iron dihydride) is an inorganic compound with the chemical formula (FeH
2)
n (also written ([FeH
2])n or FeH
2). It is a solid, known only as a black, amorphous powder, which was synthesised for the first time in 2014.[1]

Nomenclature

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

Chemical properties

In iron(II) dihydride, the atoms form a network (polymer), being connected by covalent bonds.[1] Other lower metal hydrides polymerise in a similar fashion. As of 2014, the only known method of synthesising iron dihydride, is the hydrogenation of bis(mesityl)iron under elevated pressure.[1] The amorphous form is air and water sensitive.[1]

Dihydridoiron

Dihydridoiron is a related compound with the chemical formula FeH4•
2 (also written [FeH
2]). It is a gas that cannot persist undiluted. Unsolvated dihydridoiron will spontaneously autopolymerise to oligomers. It has been observed in matrix isolation.[2] or trapped in frozen inert gases at extremely low temperatures, and dissociates into the elements in ambient conditions. It is one of the few known compounds of iron and hydrogens, and the lightest dihydride of an element from group 8 of the periodic table.

History

Even though complexes containing dihydridoiron was known since 1931,[3] the simple compound with the molecular formula FeH
2 is only a much more recent discovery. Following the discovery of the first complex containing dihydridoiron, tetracarbonylate, it was also quickly discovered that it is not possible to remove the carbon monoxide by thermal means - heating an dihydridoiron containing complex only causes it to decompose, a habit attributable to the weak iron-hydrogen bond. Thus, a practical method has been sought since then for the production of the pure compound, without the involvement of a liquid phase. Furthermore, there is also on going research into its other adducts.

Chemical Properties

Radicality

A few of dihydridoiron's electronic states lie relatively close to each other, giving rise to varying degrees of radical chemistry. The ground state and the first two excited states are all quintet radicals with four unpaired electrons (X5Δg, A5Πg, B5Σg+). With the first two excited states only 22 and 32 kJ mol−1 above the ground state, a sample of dihydridoiron contains trace quantities of excited states even at room temperature. Furthermore, Crystal field theory predicts that the low transition energies correspond to a colourless compound.

The infrared spectrum shows that the molecule has a linear H−Fe−H structure in the gas phase, with an equilibrium distance between the iron atom and the hydrogen atoms of 0.1665 nm.[2] The ground electronic state is 5Δg.[2]

 State transitions of 56FeH2 in the ν3 fundamental band[2]
Transition Wavenumber
cm−1		 Frequency
THz
P4(10) 1614.912 48.4100
P4(7) 1633.519 48.9717
Q4(4),Q3(3) 1672.658 50.1450
Q4(4),Q4(5),Q3(3) 1676.183 50.2507
R4(4) 1704.131 51.0886
R4(5) 1707.892 51.2013
R4(8) 1725.227 51.7210
R4(9) 1729.056 52.8358

Acidity

The two-coordinate hydridoiron group (-FeH) in hydridoirons such as dihydridoiron can accept an electron-pair donating ligand into the molecule by adduction:[4]

[FeH
2] + L → [FeH
2L]

Because of this acceptance of the electron-pair donating ligand (L), dihydridoiron has Lewis-acidic character. Dihydridoiron can accept four electron-pairs from ligands, as in the case of tetracarbonyldihydridoiron (FeH
2(CO)
4).

Chemical reactions

Due to the instability of this molecule and the low temperature conditions in which it is produced, and the fact that it was produced during laser ablation with two other species, FeH and FeH3, there is little known about its chemistry.

Samples trapped in frozen argon at 10 K were apparently unaffected by annealing to 30 K.[5] However the compound survives transiently at above cryogenic temperatures.

From infrared spectra of samples trapped in frozen argon between 10 and 30 K, Chertihin and Andrews conjectured in 1995 that FeH
2 readily dimerized into Fe
2H
4, and that it would react with atomic hydrogen to produce FeH
3.[5] However the identity of the latter has been questioned.[4]

Production

Dihydridoiron has been produced by several means, including:

Although iron(II) hydride has received attention only recently, complexes containing the moiety have been known at least since 1931, when iron carbonyl hydride FeH2(CO)4 was first synthesised.[7] The most precisely characterised FeH2L4 complex as of 2003 is FeH2(CO)2[P(OPh)3]2.

Complexes can also contain FeH2 with hydrogen molecules as a ligand. Those with one or two molecules of hydrogen are unstable, but FeH2(H2)3 is stable and can be produced by the evaporation of iron into hydrogen gas.[4]

References

  1. 1 2 3 4 Morris, Leah; Trudeau, Michel L.; Lees, Martin R.; Hanna, John V.; Antonelli, David M. (25 March 2014). "On the Path to Bulk FeH
    2    : Synthesis and Magnetic Properties of Amorphous Iron(II) Hydride". Journal of Alloys and Compounds. Elsevier Ltd. 590: 199–204. doi:10.1016/j.jallcom.2013.12.099.
  2. 1 2 3 4 5 Helga Körsgen, Petra Mürtz, Klaus Lipus, Wolfgang Urban, Jonathan P. Towle, John M. Brown (1996), "The identification of the FeH
    2     radical in the gas phase by infrared spectroscopy". The Journal of Chemical Physics, volume 104, issue 12, page 4859 ISSN 0021-9606 doi:10.1063/1.471180
  3. ↑ Hieber, W.; Leutert, F. (1 April 1931). "Zur kenntnis des koordinativ gebundenen kohlenoxyds: Bildung von eisencarbonylwasserstoff". Naturwissenschaften (in German). Springer-Verlag. 19 (17): 360–361. Bibcode:1931NW.....19..360H. doi:10.1007/BF01522286. ISSN 1432-1904.
  4. 1 2 3 4 Wang, Xuefeng; Lester Andrews (2009). "Infrared Spectra and Theoretical Calculations for Fe, Ru, and Os Metal Hydrides and Dihydrogen Complexes". The Journal of Physical Chemistry A. 113 (3): 551–563. doi:10.1021/jp806845h. ISSN 1089-5639.
  5. 1 2 3 George V. Chertihin and Lester Andrews (1995), "Infrared spectra of FeH, FeH
    2    , and FeH
    3     in solid argon". Journal of Physical Chemistry, volume 99, issue 32, pages 12131–12134 doi:10.1021/j100032a013
  6. ↑ Rod S. Mason and Lara J. Kelly (2012), "Synthesis of protonated ferrocene isomers in the gas phase and their study by mass spectrometry". Arkivoc, volume 2012, issue 7, pages 137-157.
  7. ↑ Hieber, W.; F. Leutert (1931). Naturwissenschaften. 18 (32): 360. Missing or empty |title= (help)
This article is issued from Wikipedia - version of the 11/26/2016. The text is available under the Creative Commons Attribution/Share Alike but additional terms may apply for the media files.