Tuesday, 25 October 2016

inorganic chemistry - What is the molecular structure of polymetatelluric acid?


Telluric Acid, Te(OH)X6, dehydrates to form polymetatelluric acid: (HX2TeOX4)X10. However, I have been unable to locate the exact structure of polymetatelluric acid, and it does not seem entirely obvious.


Are the tellurium centers connected directly to each other or are they separated by oxygen? Are these polymeric bonds single bonds or double bonds or some mixture of the two? My best guess is that the Te centers are separated by oxygens with three other oxygens surreounding each Te center, two of which are OH groups and the third being a =O group: this would make the oxygens between the Te centers alternating single and then double bonds — possibly conjugated on some level. Is there any chance polymetatelluic acid has direct TeTe bonds?



Answer



It would be ideal to check out x-ray analysis data, but it seems like polymetatelluric acid is a rather amorphous substance and does not form suitable crystals. As of now, I haven't discovered anything relevant neither in ICSD, nor in CCDC.


Another method of structural analysis would be vibrational spectroscopy. There is an article "Ultrarotspektren von Tellursäuren, Telluraten und Antimonaten" [1, p. 165] (in German) containing an extensive research of various Te-containing substances performed with infrared and Raman-spectroscopy (I reduced the table to the frequencies for polymetatelluric acid exclusively):




(HX2TeOX4)XxZuordnung450 (m,b)δ (TeO)600 (st,b,Sch)ν (TeO)720 (sst,b)600 (sst,b,Sch)1085 (mst,b)δ (TeOH)1618 (s,b)δ (HX2O)2360 (m)2δ (TeOH)3200 (sst,b)ν (TeOH)3360 (sst,b,Sch)ν (HX2O)


Polymetatellursäure (HX2TeOX4)Xx ist eine feste amorphe Substanz. In ihrem UR-Spektrum sind alle Banden sehr breit, wie man es bei amorphen Substanzen meist antrifft. Das Tellur ist in dieser Verbindung wahrscheinlich wie im Te(OH)X6 sechsfach koordiniert, wie die annähernd gleiche Lage der TeO-Valenz- und Deformationsschwingungen in beiden Verbindungen zeigt. Hieraus folgt, daß TeOTe-Bindungen vorhanden sein müssen. Bei Viererkoordination würden die Valenzschwingungen höher liegen, wie es in den vergleichbaren Molekeln IO, und HX5IOX6 der Fall ist.[...]


Im Gegensatz zum Te(OH)X6 tritt im Spektrum des (HX2TeOX4)Xx eine Frequenz bei 1618 cm1 auf, die nur von freiem Wasser herrühren kann. Ebenso beobachtet man neben der OH-Valenzschwingung der TeOH-Gruppen (3200 cm1) die Bande 3360 cm1 des freien Wassers. Aus den Intensitäten dieser Banden ist zu entnehmen, daß HX2O und TeOH-Gruppen in größenordnungsmäßig gleicher Menge vorhanden sind. Eine stöchiometrische Konstitutionsformel wird man dieser Substanz wohl nicht zuordnen können.



Briefly, the IR-spectra bands of [HX2TeOX4]x bands are very broad, suggesting amorphous non-stoichiometric compound (as Mithoron suggested) with polymeric structure where Te atom is 6-coordinated. Bands were only assigned for TeO, TeOH bonds and HX2O. IR-spectra do not show the presence of TeTe bonds. Most likely there are [TeO]X6 units with edge- or corner-sharing, linked together in a chain-alike fashion.


Reference



  1. Siebert, H. Z. anorg. allg. Chem. 1959, 301 (3–4), 161–170. DOI: 10.1002/zaac.19593010305 (in German).



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