Chemistry:Tantalum(V) ethoxide

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Tantalum(V) ethoxide
Ta2(OEt)10.png
Names
IUPAC name
Tantalum(V) ethoxide
Other names
  • Tantalum ethylate
  • Tantalum(V) ethylate
  • Pentaethyl tantalate
  • Tantalum pentaethoxide
  • Pentaethoxytantalum(V)
  • Tantalum(5+) pentaethanolate
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 228-010-2
Properties
C10H25O5Ta
Molar mass 406.25 g mol−1
Appearance Colorless liquid
Density 1.566 g/cm3 (at 25 °C)
Melting point 21 °C (70 °F; 294 K)
Boiling point 145 °C (293 °F; 418 K) at 0.0133 kPa
reacts
Solubility Organic solvents
1.488[1]
Hazards[2]
Safety data sheet External MSDS
GHS pictograms GHS02: FlammableGHS05: CorrosiveGHS07: Harmful
GHS Signal word Danger
H226, H314, H319, H335
P280, P305+351+338
NFPA 704 (fire diamond)
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilHealth code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformReactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acidNFPA 704 four-colored diamond
1
2
2
Flash point 31 °C; 87 °F; 304 K
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Tantalum(V) ethoxide is a metalorganic compound with formula Ta2(OC2H5)10, often abbreviated as Ta2(OEt)10. It is a colorless solid that dissolves in some organic solvents but hydrolyzes readily.[3] It is used to prepare films of tantalum(V) oxide.

Structure

Tantalum(V) alkoxides typically exist as dimers[4] with octahedral six-coordinate tantalum metal centres.[5] Subsequent crystallographic analysis established that the methoxide and isopropoxides of niobium adopt bioctahedral structures.[6][7] From a geometric perspective, the ten ethoxide ligand oxygen atoms of the Ta2(OEt)10 molecule in solution define a pair of octahedra sharing a common edge with the two tantalum atoms located at their centres.[6] From a bonding perspective, each tantalum centre is surrounded octahedrally by four monodentate and two bridging ethoxide ligands. The oxygen atoms of the bridging ethoxides are each bonded to both tantalum centres, and these two ligands are cis to one another within the coordination sphere. The formula [(EtO)4Ta(μ-OEt)]2 more comprehensively represents this dimeric structure, although the simplified formula is commonly used for most purposes.

Preparation

5 kg of distilled pure tantalum ethoxide, showing that it is a solid at 20 degrees C.

Several approaches are known for preparing tantalum(V) ethoxide. Salt metathesis from tantalum(V) chloride is generally the most successful. Tantalum pentachloride, Ta2Cl10, provides a convenient starting point. To avoid the generation of mixed chloride-ethoxide species, a base such as ammonia is usually added to trap liberated HCl:[8]

10 EtOH + Ta2Cl10 + 10 NH3 → Ta2(OEt)10 + 10 NH4Cl

Salt metathesis using an alkali metal alkoxide can be used as well:[8]

10 NaOEt + Ta2Cl10 → Ta2(OEt)10 + 10 NaCl

The same compound can be prepared electrochemically.[6][9] The two half-equations and the overall equation[9] for this reaction are:

cathode: 2 EtOH + 2 e− → 2 EtO− + H2
anode: Ta → "Ta5+" + 5 e−
overall: 2 Ta + 10 EtOH → 2 "Ta5+" + 10 EtO− + 5 H2 → Ta2(OEt)10 + 5 H2

Commercial production of tantalum(V) ethoxide using this electrochemical approach has been employed in Russia.[9] The compound can also be prepared by direct reaction of tantalum metal with ethanol, in which case the overall equation is the same as that shown above for the electrochemical approach.[8]

Since the 1970s, Bayer of Germany had been producing tantalum (V) ethoxide in Leverkusen, however following the break-up of Bayer, production moved to Heraeus. Meanwhile, Inorgtech (later MultiValent), started production in 1974 in Cambridge, UK. Both routes involved the direct reaction of the metal chloride with alcohol in the presence of solvents to give a product of 99.999%+ purity.[citation needed]

Reactions

The most important reaction of tantalum alkoxides is hydrolysis to produce films and gels of tantalum oxides. Although these reactions are complex, the formation of a tantalum(V) oxide film by hydrolysis[3] can be described by this simplified equation:

Ta2(OC2H5)10 + 5 H2O → Ta2O5 + 10 C2H5OH

Tantalum(V) ethoxide optical coatings can be produced by low pressure chemical vapour deposition.[10] At pressures as low as 1.33 mPa and temperatures of 700 °C, a silica film of the desired depth is first deposited by the decomposition of tetraethoxysilane, Si(OEt)4, or di-t-butyoxydiacetoxysilane, Si(OC(CH3)3)2(OOCCH3)2, then tantalum(V) ethoxide is introduced.[10] As in the case of niobium(V) ethoxide, the ethoxide precursor thermally decomposes to produce the oxide layer with the associated release of diethyl ether:

Ta2(OEt)10 → Ta2O5 + 5 Et–O–Et

Pyrolysis also produces a tantalum(V) oxide film by chemical vapor deposition in which case the tantalum(V) ethoxide is completely oxidised, producing carbon dioxide and water vapor:[11]

Ta2(OC2H5)10 + 30 O2 → Ta2O5 + 20 CO2 + 25 H2O

Amorphous tantalum(V) oxide films can also be prepared by atomic layer deposition or by a pulsed chemical vapour deposition technique in which tantalum(V) ethoxide and tantalum(V) chloride are applied alternately.[12] At temperatures approaching 450 °C the films produced have refractive indices and permittivity properties similar to those produced from conventional approaches.[12] The preparation of these films occurs with the loss of chloroethane:[12]

Ta2(OC2H5)10 + Ta2Cl10 → 2 Ta2O5 + 10 C2H5Cl

Sol-gel processing also produces thin films of tantalum(V) oxide[13] using a similar chemical approach. Sol-gel routes using tantalum(V) ethoxide to generate layered perovskite materials have also been developed.[14]

Applications

It is mainly used for the manufacture of tantalum(V) oxide thin-film materials by approaches including chemical vapor deposition,[10] atomic layer deposition,[12] and sol-gel processing.[13] These materials have semiconductor,[12] electrochromic,[15] and optical[10] applications.

Tantalum(V) oxide films have a variety of applications including as optical films with refractive indices as high as 2.039[16] and as a thin-film dielectric material in dynamic random access memory and semiconductor field-effect transistors.[12] The approach chosen for preparation of these materials is determined by the desired properties. Direct hydrolysis is appropriate when the presence of residual water or the use of high temperatures for drying is acceptable. Micropatterns can be produced by site-selective deposition using the hydrolysis approach by forming a self-assembled monolayer followed by high temperature annealling.[17] Chemical vapour deposition allows control of the thickness of the film on a nanometre scale, which is essential for some applications. Direct pyrolysis is convenient for optical applications,[10] where transparent materials with low light loss due to absorption is important,[16] and has also been used to prepare nitride read-only memory.[11] Electrochromism is the property of some materials to change color when charge is applied,[18] and is the means by which so-called smart glass operates. Films produced by tantalum(V) ethoxide hydrolysis has been used to prepare amorphous tantalum(V) oxide films suitable for electrochromic applications.[15]

Mixed-metal thin-films have also been prepared from this compound. For example, lithium tantalate, LiTaO3, films are desirable for their non-linear optical properties and have been prepared by first reacting tantalum(V) ethoxide with lithium dipivaloylmethanate, LiCH(COC(CH3)3)2, to prepare a precursor suitable for metalorganic vapour phase epitaxy (a form of chemical vapor deposition).[19] Films of strontium tantalate, Sr(TaO3)2, have also been prepared using atomic layer deposition approaches and their properties investigated.[20]

Tantalum(V) ethoxide condenses with carboxylic acids to give oxo-alkoxide-carboxylates, e.g., Ta4O4(OEt)8(OOCCH3)4.[8] The Ta4O4 core of such compounds form a cubane-type cluster.

References

  1. ↑ "Tantalum Ethoxide and Niobium Ethoxide". Materian Advanced Chemicals. http://worldwide.espacenet.com/publicationDetails/description?CC=US&NR=2012244062A1&KC=A1&FT=D&ND=4&date=20120927&DB=EPODOC&locale=en_EP. Retrieved 19 October 2012. 
  2. ↑ "Tantalum (V) ethoxide 99.98% trace metals basis". Sigma Aldrich. http://www.sigmaaldrich.com/catalog/product/aldrich/339113?lang=en&region=US. Retrieved 18 October 2012. 
  3. ↑ 3.0 3.1 Lide, David R., ed (2006). CRC Handbook of Chemistry and Physics (87th ed.). Boca Raton, FL: CRC Press. ISBN 0-8493-0487-3. 
  4. ↑ Bradley, D. C.; Holloway, C. E. (1968). "Nuclear Magnetic Resonance Studies on Niobium and Tantalum Penta-alkoxides". J. Chem. Soc. A: 219–223. doi:10.1039/J19680000219. 
  5. ↑ Bradley, D. C.; Holloway, H. (1961). "Metal Oxide Alkoxide Polymers: Part II. The Hydrolysis Of Tantalum Pentaethoxide". Can. J. Chem. 39 (9): 1818–1826. doi:10.1139/v61-239. 
  6. ↑ 6.0 6.1 6.2 Turova, N. Y.; Korolev, A. V.; Tchebukov, D. E.; Belokon, A. I.; Yanovsky, A. I.; Struchkov, Y. T. (1996). "Tantalum(V) Alkoxides: Electrochemical Synthesis, Mass-Spectral Investigation and Oxoalkoxocomplexes". Polyhedron 15 (21): 3869–3880. doi:10.1016/0277-5387(96)00092-7. 
  7. ↑ Mehrotra, Ram C.; Singh, Anirudh (1997). "Recent Trends in Metal Alkoxide Chemistry". in Karlin, Kenneth D.. Progress in Inorganic Chemistry. 46. John Wiley & Sons. pp. 239–454. doi:10.1002/9780470166475.ch4. ISBN 9780470167045. https://books.google.com/books?id=Pui4TU1yzYkC&pg=PA239. 
  8. ↑ 8.0 8.1 8.2 8.3 Schubert, U. (2003). "Sol–Gel Processing of Metal Compounds". in McCleverty, J. A.; Meyer, T. J.. Comprehensive Coordination Chemistry II. Reference Module in Chemistry, Molecular Sciences and Chemical Engineering. 7. Pergamon. pp. 629–656. doi:10.1016/B0-08-043748-6/06213-7. ISBN 978-0-12-409547-2. 
  9. ↑ 9.0 9.1 9.2 Bradley, Don C.; Mehrotra, Ram C.; Rothwell, Ian P.; Singh, A. (2001). Alkoxo and Aryloxo Derivatives of Metals. San Diego: Academic Press. p. 18. ISBN 978-0-08-048832-5. https://books.google.com/books?id=noeJ0u7mOoIC&pg=PA18. 
  10. ↑ 10.0 10.1 10.2 10.3 10.4 Baumeister, P. W. (2004). Optical Coating Technology. SPIE Press. p. 7. ISBN 9780819453136. https://books.google.com/books?id=3TXqjrlDRQcC&pg=RA1-PA7. 
  11. ↑ 11.0 11.1 & Chen, C.-H."Method For Fabricating A Nitride Read-Only-Memory (NROM)" US patent 6461949, issued 2002-10-08, assigned to Macronix International Co. Ltd.
  12. ↑ 12.0 12.1 12.2 12.3 12.4 12.5 Kukli, K.; Ritala, M.; Leskelä, M. (2000). "Atomic Layer Deposition and Chemical Vapor Deposition of Tantalum Oxide by Successive and Simultaneous Pulsing of Tantalum Ethoxide and Tantalum Chloride". Chem. Mater. 12 (7): 1914–1920. doi:10.1021/cm001017j. 
  13. ↑ 13.0 13.1 Winter, S.; Velten, D.; Aubertin, F.; Hoffmann, B.; Heidenau, F.; Ziegler, G. (2008). "Chemical Surface Modifications". in Breme, J.; Kirkpatrick, C. J.; Thull, R.. Metallic Biomaterial Interfaces. John Wiley & Sons. p. 51. ISBN 9783527318605. https://books.google.com/books?id=CInt3HXtIuMC&pg=PA51. 
  14. ↑ Nalwa, H. S. (2001). Handbook of Advanced Electronic and Photonic Materials and Devices: Chalcogenide Glasses and Sol-Gel Materials. Academic Press. p. 208. ISBN 9780125137553. https://books.google.com/books?id=soZUAAAAMAAJ&q=tantalum(V)+ethoxide. 
  15. ↑ 15.0 15.1 Tepehan, F. Z.; Ghodsi, F. E.; Ozer, N.; Tepehan, G. G. (1999). "Optical Properties Of Sol-Gel Dip-Coated Ta2O5 Films For Electrochromic Applications". Solar Energy Materials and Solar Cells 59 (3): 265–275. doi:10.1016/S0927-0248(99)00041-0. 
  16. ↑ 16.0 16.1 Oubaha, M.; Elmaghrum, S.; Copperwhite, R.; Corcoran, B.; McDonagh, C.; Gorin, A. (2012). "Optical Properties of High Refractive Index Thin Films Processed at Low-Temperature". Opt. Mater. 34 (8): 1366–1370. doi:10.1016/j.optmat.2012.02.023. Bibcode: 2012OptMa..34.1366O. https://arrow.dit.ie/cgi/viewcontent.cgi?article=1067&context=cenresart. 
  17. ↑ Masuda, Y.; Wakamatsu, S.; Koumoto, K. (2004). "Site-Selective Deposition And Micropatterning Of Tantalum Oxide Thin Films Using A Monolayer". J. Eur. Ceram. Soc. 24 (2): 301–307. doi:10.1016/S0955-2219(03)00230-9. 
  18. ↑ Mortimer, R. J. (2011). "Electrochromic Materials". Annu. Rev. Mater. Res. 41 (Pt 3): 241–268. doi:10.1146/annurev-matsci-062910-100344. PMID 12449538. Bibcode: 2011AnRMS..41..241M. 
  19. ↑ Wernberg, A. A.; Braunstein, G.; Paz-Pujalt, G.; Gysling, H. J.; Blanton, T. N. (1993). "Solid-Phase Epitaxial-Growth Of Lithium Tantalate Thin-Films Deposited By Spray-Metalorganic Chemical-Vapor-Deposition". Appl. Phys. Lett. 63 (3): 331–333. doi:10.1063/1.110061. Bibcode: 1993ApPhL..63..331W. 
  20. ↑ Lee, W. J.; You, I. K.; Ryu, S. O.; Yu, B. G.; Cho, K. I.; Yoon, S. G.; Lee, C. S. (2001). "SrTa2O6 Thin Films Deposited By Plasma-Enhanced Atomic Layer Deposition". Jpn. J. Appl. Phys. 40 (12): 6941–6944. doi:10.1143/JJAP.40.6941. Bibcode: 2001JaJAP..40.6941L. 



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