Zinc hydride

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Zinc hydride
Identifiers
CAS number 14018-82-7 YesY
PubChem 22056524
ChemSpider 10806557 N
Jmol-3D images Image 1
Properties
Molecular formula ZnH
2
Molar mass 67.425 g mol-1
Appearance White crystals
Related compounds
Related compounds Mercury(II) hydride
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Zinc hydride is an inorganic compound with the chemical formula ZnH2. It is a white, odourless solid which slowly decomposes into its elements at room temperature; despite this it is the most stable of the binary first row transition metal hydrides. A variety of coordination compounds containing Zn-H bonds are used as reducing agents,[1] however ZnH2 itself has no common applications.

Discovery and synthesis[edit]

Zinc(II) hydride was first synthesised in 1947 by Hermann Schlesinger, via a reaction between dimethylzinc and lithium aluminium hydride;[2] a process which was somewhat hazardous due to the pyrophoric nature of Zn(CH3)2.

Zn(CH3)2 + 2 LiAlH4 → ZnH2 + 2 LiAlH3CH3

Later methods were predominantly salt metathesis reactions between zinc halides and alkali metal hydrides, which are significantly safer.[3][4] Examples include:

ZnBr2 + 2LiH → ZnH2 + 2LiBr
ZnI2 + 2 NaH + → ZnH2 + 2NaI
ZnI2 + 2 LiAlH4 → ZnH2 + AlH3 + 2LiI

Small quantities of gaseous zinc(II) hydride have also been produced by laser ablation of zinc under a hydrogen atmosphere[5][6] and other high energy techniques. These methods have been used to assess its gas phase properties.

Chemical properties[edit]

Structure[edit]

New evidence suggests that in zinc(II) hydride, elements form a one-dimensional network (polymer), being connected by covalent bonds.[7] Other lower metal hydrides polymerise in a similar fashion (c.f. aluminium hydride). Solid zinc(II) hydride is the irreversible autopolymerisation product of the molecular form, and the molecular form cannot be isolated in concentration. Solubilising zinc(II) hydride in non-aqueous solvents, involve adducts with molecular zinc(II) hydride, such as ZnH2(H2) in liquid hydrogen.

Stability[edit]

Zinc(II) hydride slowly decomposes to metallic zinc and H2 at room temperature, with decomposition becoming rapid if it is heated above 90°C.[8]

ZnH2 → H2 + Zn0

It is readily oxidised and is sensitive to both air and moisture; being hydrolysed slowly by water but violently by aqueous acids,[3] which indicates possible passivation via the formation of a surface layer of ZnO. Despite this older samples may be pyrophoric.[3] Zinc hydride can therefore be considered metastable at best, however it is still the most stable of all the binary first row transition metal hydrides (c.f. titanium(IV) hydride).

Molecular form[edit]

Molecular zinc(II) hydride, ZnH2, was recently identified as a volatile product of the acidified reduction of zinc ions with sodium borohydride.[citation needed] This reaction is similar to the acidified reduction with lithium aluminium hydride, however a greater fraction of the generated zinc(II) hydride is in the molecular form. This can be attributed to a slower reaction rate, which prevents a polymerising concentration of building over the progression of the reaction. This follows earlier experiments in direct synthesis from the elements. The reaction of excited zinc atoms with molecular hydrogen in the gas phase was studied by Breckenridge et al using laserpump-probe techniques.[citation needed] Owing to its relative thermal stability, molecular zinc(II) hydride is included in the short list of molecular metal hydrides, which have been successfully identified in the gas phase (that is, not limited to matrix isolation).

The average Zn-H bond energy was recently calculated to be 51.24 kcal mol−1, while the H-H bond energy is 103.3 kcal mol−1.[citation needed] Therefore, the overall reaction is nearly ergoneutral.

Zn(g) + H2(g) → ZnH2(g)

Molecular zinc hydride in the gas phase was found to be linear with a Zn-H bond length of 153.5 pm.[9]

The molecule can be found a singlet ground state of 1Σg+.

Quantum chemical calculations predict the molecular form to exist in a doubly hydrogen-bridged, dimeric groundstate, with little or no formational energy barrier.[citation needed]The dimer can be described as di-μ-hydrido-bis(hydridozinc), according to IUPAC additive nomenclature.

References[edit]

  1. ^ Enthaler, Stephan (1 February 2013). "Rise of the Zinc Age in Homogeneous Catalysis?". ACS Catalysis 3 (2): 150–158. doi:10.1021/cs300685q. 
  2. ^ A. E. Finholt, A. C. Bond, Jr., H. I. Schlesinger (1947). "Lithium Aluminum Hydride, Aluminum Hydride and Lithium Gallium Hydride, and Some of their Applications in Organic and Inorganic Chemistry". Journal of the American Chemical Society 69 (5): 1199–1203. doi:10.1021/ja01197a061. 
  3. ^ a b c Herrmann, Wolfgang A. (1997). Synthetic Methods of Organometallic and Inorganic Chemistry. Georg Thieme Verlag. ISBN 3-13-103061-5. 
  4. ^ Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0-12-352651-5
  5. ^ Greene, Tim M.; Brown, Wendy; Andrews, Lester; Downs, Anthony J.; Chertihin, George V.; Runeberg, Nino; Pyykko, Pekka (1 May 1995). "Matrix Infrared Spectroscopic and ab Initio Studies of ZnH2, CdH2, and Related Metal Hydride Species". The Journal of Physical Chemistry 99 (20): 7925–7934. doi:10.1021/j100020a014. 
  6. ^ Wang, Xuefeng; Andrews, Lester (2004). "Infrared Spectra of Zn and Cd Hydride Molecules and Solids". The Journal of Physical Chemistry A 108 (50): 11006–11013. doi:10.1021/jp046414m. ISSN 1089-5639. 
  7. ^ Grochala, Wojciech; Edwards, Peter P. (18 February 2004). "Thermal decomposition of the non-interstitial hydrides for the storage and production of hydrogen". Chemical Reviews 104 (3): 1283–1316. doi:10.1021/cr030691s. PMID 15008624. Retrieved 16 June 2013. 
  8. ^ Synthetic methods of organometallic and inorganic chemistry. Stuttgart: Thieme. 1999. p. 115. ISBN 9783131030610. 
  9. ^ Shayesteh, Alireza; Appadoo, Dominique R. T.; Gordon, Iouli E.; Bernath, Peter F.; Journal of the American Chemical Society (2004). "Vibration−Rotation Emission Spectra of Gaseous ZnH2 and ZnD2". Journal of the American Chemical Society 126 (44): 14356–14357. doi:10.1021/ja046050b. PMID 15521746.