Germanium compounds

Germanium compounds are chemical compounds formed by the element germanium (Ge). Germanium is insoluble in dilute acids and alkalis but dissolves slowly in hot concentrated sulfuric and nitric acids and reacts violently with molten alkalis to produce germanates ([GeO
3]2−
). Germanium occurs mostly in the oxidation state +4 although many +2 compounds are known.[1] Other oxidation states are rare: +3 is found in compounds such as Ge2Cl6, and +3 and +1 are found on the surface of oxides,[2] or negative oxidation states in germanides, such as −4 in Mg
2Ge. Germanium cluster anions (Zintl ions) such as Ge42−, Ge94−, Ge92−, [(Ge9)2]6− have been prepared by the extraction from alloys containing alkali metals and germanium in liquid ammonia in the presence of ethylenediamine or a cryptand.[1][3] The oxidation states of the element in these ions are not integers—similar to the ozonides O3−.

Chalcogenides

Oxides

Two oxides of germanium are known: germanium dioxide (GeO
2, germania) and germanium monoxide, (GeO).[4] The dioxide, GeO2 can be obtained by roasting germanium disulfide (GeS
2) or by allowing elemental germanium to slowly oxidze in air,[5] and is a white powder that is only slightly soluble in water but reacts with alkalis to form germanates.[4] The monoxide, germanous oxide, can be obtained by the high temperature reaction of GeO2 with Ge metal.[4] The dioxide (and the related oxides and germanates) exhibits the unusual property of having a high refractive index for visible light, but transparency to infrared light.[6][7] Bismuth germanate, Bi4Ge3O12, (BGO) is used as a scintillator.[8]

Other chalcogenides

Binary compounds with other chalcogens are also known, such as the disulfide (GeS
2), diselenide (GeSe
2), and the monosulfide (GeS), selenide (GeSe), and telluride (GeTe).[1] GeS2 forms as a white precipitate when hydrogen sulfide is passed through strongly acid solutions containing Ge(IV).[1] The disulfide is appreciably soluble in water and in solutions of caustic alkalis or alkaline sulfides. Nevertheless, it is not soluble in acidic water, which allowed Winkler to discover the element.[9] By heating the disulfide in a current of hydrogen, the monosulfide (GeS) is formed, which sublimes in thin plates of a dark color and metallic luster, and is soluble in solutions of the caustic alkalis.[4] Upon melting with alkaline carbonates and sulfur, germanium compounds form salts known as thiogermanates.[10]

Hydrides

Skeletal chemical structure of a tetrahedral molecule with germanium atom in its center bonded to four hydrogen atoms. The Ge-H distance is 152.51 picometers.
Germane is similar to methane.

Germane (GeH4) is a compound similar in structure to methane. Polygermanes—compounds that are similar to alkanes—with formula GenH2n+2 containing up to five germanium atoms are known.[1] The germanes are less volatile and less reactive than their corresponding silicon analogues.[1] GeH4 reacts with alkali metals in liquid ammonia to form white crystalline MGeH3 which contain the GeH3− anion.[1] The germanium hydrohalides with one, two and three halogen atoms are colorless reactive liquids.[1]

Halides

Four tetrahalides are known. Under normal conditions GeI4 is a solid, GeF4 a gas and the others volatile liquids. For example, germanium tetrachloride, GeCl4, is obtained as a colorless fuming liquid boiling at 83.1 °C by heating the metal with chlorine.[4] All the tetrahalides are readily hydrolyzed to hydrated germanium dioxide.[4] GeCl4 is used in the production of organogermanium compounds.[1] All four dihalides are known and in contrast to the tetrahalides are polymeric solids.[1] Additionally Ge2Cl6 and some higher compounds of formula GenCl2n+2 are known.[4] The unusual compound Ge6Cl16 has been prepared that contains the Ge5Cl12 unit with a neopentane structure.[11]

Organogermanium compounds

Main article: Organogermanium chemistry
Skeletal chemical structures outlining an additive chemical reaction including an organogermanium compound.
Nucleophilic addition with an organogermanium compound.

The first organogermanium compound was synthesized by Winkler in 1887; the reaction of germanium tetrachloride with diethylzinc yielded tetraethylgermane (Ge(C
2H
5)
4).[12] Organogermanes of the type R4Ge (where R is an alkyl) such as tetramethylgermane (Ge(CH
3)
4) and tetraethylgermane are accessed through the cheapest available germanium precursor germanium tetrachloride and alkyl nucleophiles. Organic germanium hydrides such as isobutylgermane ((CH
3)
2CHCH
2GeH
3) were found to be less hazardous and may be used as a liquid substitute for toxic germane gas in semiconductor applications. Many germanium reactive intermediates are known: germyl free radicals, germylenes (similar to carbenes), and germynes (similar to carbynes).[13][14] The organogermanium compound 2-carboxyethylgermasesquioxane was first reported in the 1970s, and for a while was used as a dietary supplement and thought to possibly have anti-tumor qualities.[15]

Using a ligand called Eind (1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) germanium is able to form a double bond with oxygen (germanone). Germanium hydride and alkylgermanes are very flammable and even explosive when mixed with air.[16]

See also

References

  1. ^ a b c d e f g h i j Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  2. ^ Tabet, N; Salim, M. A.; Al-Oteibi, A. L. (1999). "XPS study of the growth kinetics of thin films obtained by thermal oxidation of germanium substrates". Journal of Electron Spectroscopy and Related Phenomena. 101–103: 233–238. doi:10.1016/S0368-2048(98)00451-4.
  3. ^ Xu, Li; Sevov, Slavi C. (1999). "Oxidative Coupling of Deltahedral [Ge9]4− Zintl Ions". J. Am. Chem. Soc. 121 (39): 9245–9246. doi:10.1021/ja992269s.
  4. ^ a b c d e f g Holleman, A. F.; Wiberg, E.; Wiberg, N. (2007). Lehrbuch der Anorganischen Chemie (102nd ed.). de Gruyter. ISBN 978-3-11-017770-1. OCLC 145623740.
  5. ^ Tabet, N; Salim, Mushtaq A. (1998). "KRXPS study of the oxidation of Ge(001) surface". Applied Surface Science. 134 (1–4): 275–282. Bibcode:1998ApSS..134..275T. doi:10.1016/S0169-4332(98)00251-7.
  6. ^ Bayya, Shyam S.; Sanghera, Jasbinder S.; Aggarwal, Ishwar D.; Wojcik, Joshua A. (2002). "Infrared Transparent Germanate Glass-Ceramics". Journal of the American Ceramic Society. 85 (12): 3114–3116. doi:10.1111/j.1151-2916.2002.tb00594.x.
  7. ^ Drugoveiko, O. P.; Evstrop'ev, K. K.; Kondrat'eva, B. S.; Petrov, Yu. A.; Shevyakov, A. M. (1975). "Infrared reflectance and transmission spectra of germanium dioxide and its hydrolysis products". Journal of Applied Spectroscopy. 22 (2): 191–193. Bibcode:1975JApSp..22..191D. doi:10.1007/BF00614256. S2CID 97581394.
  8. ^ Lightstone, A. W.; McIntyre, R. J.; Lecomte, R.; Schmitt, D. (1986). "A Bismuth Germanate-Avalanche Photodiode Module Designed for Use in High Resolution Positron Emission Tomography". IEEE Transactions on Nuclear Science. 33 (1): 456–459. Bibcode:1986ITNS...33..456L. doi:10.1109/TNS.1986.4337142. S2CID 682173.
  9. ^ Johnson, Otto H. (1952). "Germanium and its Inorganic Compounds". Chem. Rev. 51 (3): 431–469. doi:10.1021/cr60160a002.
  10. ^ Fröba, Michael; Oberender, Nadine (1997). "First synthesis of mesostructured thiogermanates". Chemical Communications (18): 1729–1730. doi:10.1039/a703634e.
  11. ^ Beattie, I.R.; Jones, P.J.; Reid, G.; Webster, M. (1998). "The Crystal Structure and Raman Spectrum of Ge5Cl12·GeCl4 and the Vibrational Spectrum of Ge2Cl6". Inorg. Chem. 37 (23): 6032–6034. doi:10.1021/ic9807341. PMID 11670739.
  12. ^ Winkler, Clemens (1887). "Mittheilungen über des Germanium. Zweite Abhandlung". J. Prak. Chemie (in German). 36 (1): 177–209. doi:10.1002/prac.18870360119. Archived from the original on 2012-11-03. Retrieved 2008-08-20.
  13. ^ Satge, Jacques (1984). "Reactive intermediates in organogermanium chemistry". Pure Appl. Chem. 56 (1): 137–150. doi:10.1351/pac198456010137. S2CID 96576323.
  14. ^ Quane, Denis; Bottei, Rudolph S. (1963). "Organogermanium Chemistry". Chemical Reviews. 63 (4): 403–442. doi:10.1021/cr60224a004.
  15. ^ Tao, S. H.; Bolger, P. M. (June 1997). "Hazard Assessment of Germanium Supplements". Regulatory Toxicology and Pharmacology. 25 (3): 211–219. doi:10.1006/rtph.1997.1098. PMID 9237323. Archived from the original on 2020-03-10. Retrieved 2019-06-30.
  16. ^ Broadwith, Phillip (25 March 2012). "Germanium-oxygen double bond takes centre stage". Chemistry World. Archived from the original on 2014-05-17. Retrieved 2014-05-15.

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