:Tellurate
{{short description|Compound containing an oxyanion of tellurium}}
In chemistry, tellurate is a compound containing an oxyanion of tellurium where tellurium has an oxidation number of +6. In the naming of inorganic compounds it is a suffix that indicates a polyatomic anion with a central tellurium atom.[http://old.iupac.org/publications/books/rbook/Red_Book_2005.pdf Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005] – Full text (PDF)
Tellurium oxyanions
Historically the name tellurate was only applied to oxyanions of tellurium with oxidation number +6, formally derived from telluric acid {{chem2|Te(OH)6}}, and the name tellurite referred to oxyanions of tellurium with oxidation number +4, formally derived from tellurous acid {{chem2|(HO)2TeO}} and these names are in common use. However tellurate and tellurite are often referred to as tellurate(VI) and tellurate(IV) respectively in line with IUPAC renaming recommendations.
The metatellurate ion is {{chem|TeO|4|2−}} and the orthotellurate ion is {{chem|TeO|6|6−}}. Other oxyanions include pentaoxotellurate, {{chem|TeO|5|4−}},{{cite journal|last1=Untenecker|first1=H.|last2=Hoppe|first2=R.|title=Die koordinationszahl 5 bei telluraten: Cs2K2[TeO5]|journal=Journal of the Less Common Metals|volume=124|issue=1–2|year=1986|pages=29–40|issn=0022-5088|doi=10.1016/0022-5088(86)90474-1}} ditellurate, {{chem|Te|2|O|10|8−}}Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications {{ISBN|0-19-855370-6}} and polymeric anions with 6-coordinate tellurium such as ({{chem|TeO|5|4−}})n.{{cite journal|last1=Weil|first1=Matthias|title=Preparation, Thermal Behaviour and Crystal Structure of the Basic Mercury(II) Tetraoxotellurate(VI), Hg2TeO5, and Redetermination of the Crystal Structure of Mercury(II) Orthotellurate(VI), Hg3TeO6|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=629|issue=4|year=2003|pages=653–657|issn=0044-2313|doi=10.1002/zaac.200390111}}
=Metatellurates=
The metatellurate ion {{chem|TeO|4|2−}} is analogous to the sulfate ion, {{chem|SO|4|2−}} and the selenate ion, {{chem|SeO|4|2−}}. Whereas many sulfates and selenates form isomorphous salts{{Cotton&Wilkinson6th|pages = 531}} the tetrahedral metatellurate ion is only found in a few compounds such as the tetraethylammonium salt {{chem2|(NEt4)2TeO4}}.{{cite journal|last1=Konaka|first1=Saki|last2=Ozawa|first2=Yoshiki|last3=Yagasaki|first3=Atsushi|title=Tetrahedral Tellurate|journal=Inorganic Chemistry|volume=47|issue=4|year=2008|pages=1244–1245|issn=0020-1669|doi=10.1021/ic701578p|pmid=18220344}} Many compounds with a stoichiometry that suggests the presence of a metatellurate ion actually contain polymeric anions containing 6-coordinate tellurium(VI), for example sodium tellurate, {{chem2|Na2TeO4}} which contains octahedral tellurium centers sharing edges.{{cite journal|last1=Kratochvíl|first1=B.|last2=Jenšovský|first2=L.|title=The crystal structure of sodium metatellurate|journal=Acta Crystallographica Section B|volume=33|issue=8|year=1977|pages=2596–2598|issn=0567-7408|doi=10.1107/S0567740877008978|doi-access=}}
:{{chem|TeO|4|2−}} → {{chem|TeO|3|2−}} + {{1/2}} O2{{spaces|5}} (E0 = −1.042 V)
The E0 or standard reduction potential value is significant as it gives an indication of the strength of the tellurate ion as an oxidizing agent.
=Orthotellurates=
Compounds containing the octahedral {{chem|TeO|6|6−}} anion are known, these include {{chem2|Ag6TeO6}}, {{chem2|Na6TeO6}} and {{chem2|Hg3TeO6}}.{{Holleman&Wiberg|pages = 593}} There are also hydroxyoxotellurates, containing protonated {{chem|TeO|6|6−}}, such as {{chem2|(NH4)2TeO2(OH)4}} (sometimes written as {{chem2|NH4TeO4*2H2O}}) which contains the octahedral {{chem|TeO|2|(OH)|4|2−}} ion.{{cite journal|last1=Johansson|first1=G. B.|last2=Lindqvist|first2=O.|last3=Moret|first3=J.|title=Diammonium tellurium(VI) dioxide tetrahydroxide|journal=Acta Crystallographica Section B|volume=35|issue=7|year=1979|pages=1684–1686|issn=0567-7408|doi=10.1107/S056774087900741X|url=http://journals.iucr.org/b/issues/1979/07/00/a17652/a17652.pdf}}
={{chem|TeO|5|4−}} ion =
The compound {{chem2|Cs2K2TeO5}} contains {{chem|TeO|5|4−}} ions which are trigonal bipyramidal. The compound {{chem2|Rb6Te2O9}} contains both {{chem|TeO|5|4−}} and {{chem|TeO|4|2−}} anions.{{Greenwood&Earnshaw|page = 782}} Other compounds whose stoichiometry suggests the presence of {{chem|TeO|5|4−}} may contain either the dimeric {{chem|Te|2|O|10|8−}} made up of two edge-sharing {TeO6} as in {{chem2|Li4TeO5}} and {{chem2|Ag4TeO5}}{{cite journal|last1=Weil|first1=Matthias|title=New Silver Tellurates – The Crystal Structures of a Third Modification of Ag2Te2O6 and of Ag4TeO5|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=633|issue=8|year=2007|pages=1217–1222|issn=0044-2313|doi=10.1002/zaac.200700106}} or corner-sharing {TeO6} octahedra as in {{chem2|Hg2TeO5}}.
=Polymeric tellurate ions=
The dimeric {{chem|Te|2|O|10|8−}} made up of two edge sharing {TeO6} octahedra is found in the compound {{chem2|Li4TeO5}}. A similar hydroxy-oxy anion, {{chem2|Te2O6(OH)4}} is found in sodium potassium ditellurate(VI) hexahydrate, {{chem2|Na0.5K3.5Te2O6(OH)4*6H2O}} which contains pairs of edge sharing octahedra.{{cite journal|last1=Kratochvíl|first1=B.|last2=Podlahová|first2=J.|last3=Jenšovský|first3=L.|title=Sodium potassium ditellurate(VI) hexahydrate|journal=Acta Crystallographica Section B|volume=34|issue=1|year=1978|pages=256–258|issn=0567-7408|doi=10.1107/S056774087800271X|doi-access=}}
Polymeric chain anions consisting of corner-shared {TeO6} octahedra ({{chem2|TeO5}}){{su|b=n|p=4n−}} are found, for example in {{chem2|Li4TeO5}}.
=Aqueous chemistry=
In aqueous solution tellurate ions are 6 coordinate. In neutral conditions the pentahydrogen orthotellurate ion, {{chem|H|5|TeO|6|−}}, is the most common; in basic conditions, the tetrahydrogen orthotellurate ion, {{chem|H|4|TeO|6|2−}}, and in acid conditions, orthotelluric acid, {{chem2|Te(OH)6}} or {{chem2|H6TeO6}} is formed.{{cite journal|last1=Frost|first1=Ray L.|title=Tlapallite H6(Ca,Pb)2(Cu,Zn)3SO4(TeO3)4TeO6, a multi-anion mineral: A Raman spectroscopic study|journal=Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy|volume=72|issue=4|year=2009|pages=903–906|issn=1386-1425|doi=10.1016/j.saa.2008.12.008|pmid=19167264|bibcode=2009AcSpA..72..903F|url=https://eprints.qut.edu.au/17594/1/17594.pdf}}
=Structural comparisons with oxyanions of sulfur and selenium=
Sulfur(VI) oxyanions have a coordination number of 4 and in addition to the tetrahedral sulfate ion, {{chem|SO|4|2−}}, the pyrosulfate, {{chem|S|2|O|7|2−}}, trisulfate, {{chem|S|3|O|10|2−}} and pentasulfate {{chem|S|5|O|16|2−}} ions all contain 4-coordinate sulfur and are built from corner-shared {{chem2|{SO4}|}} tetrahedra.{{Greenwood&Earnshaw|page = 712}} Selenate compounds include many examples of four coordinate selenium, principally the tetrahedral {{chem|SeO|4|2−}} ion and the pyroselenate ion, {{chem|Se|2|O|7|2−}} which has a similar structure to the pyrosulfate ion.{{cite journal|last1=Paetzold|first1=R.|last2=Amoulong|first2=H.|last3=Růžička|first3=A.|title=Untersuchungen an Selen-Sauerstoff-Verbindungen. XXVI. Schwingungsspektrum und Kraftkonstanten des Diselenations|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=336|issue=5–6|year=1965|pages=278–285|issn=0044-2313|doi=10.1002/zaac.19653360508}} Unlike sulfur there are examples of a 5-coordinate selenium oxyanion, {{chem|SeO|5|4−}} and one example of {{chem|SeO|6|6−}}.{{cite journal|last1=Haas|first1=Helmut|last2=Jansen|first2=Martin|title=Octahedral SeO66− and Square-Pyramidal SeO54−, Two New Oxoselenate Anions|journal=Angewandte Chemie|volume=39|issue=23|year=2000|pages=4362–4364|issn=1433-7851|doi=10.1002/1521-3773(20001201)39:23<4362::AID-ANIE4362>3.0.CO;2-S}}{{cite journal|last1=Orosel|first1=Denis|last2=Dinnebier|first2=Robert|last3=Jansen|first3=Martin|title=High-Pressure Synthesis and Structure Determination of K6(SeO4)(SeO5), the First Potassium Orthoselenate(VI)|journal=Inorganic Chemistry|volume=45|issue=26|year=2006|pages=10947–10950|issn=0020-1669|doi=10.1021/ic061548v|pmid=17173453}}{{cite journal|last1=Haas|first1=H.|last2=Jansen|first2=M.|title=Na4SeO5, ein neues Pentaoxoselenat(VI) – Synthese, Charakterisierung und Vergleich mit isotypem Na4MoO5|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=627|issue=4|year=2001|pages=755–760|issn=0044-2313|doi=10.1002/1521-3749(200104)627:4<755::AID-ZAAC755>3.0.CO;2-L}}
NMR spectroscopy
Tellurium has two NMR active nuclei, 123Te and 125Te. 123Te has an abundance of 0.9% and a nuclear spin ({{mvar|I}}) of {{sfrac|1|2}}. 125Te has an abundance of 7% and an equivalent nuclear spin.{{Housecroft3rd}} 125Te is more commonly performed because it has a higher sensitivity.Drago, R. S. Physical Methods for Chemists 2nd ed.; Surfside Scientific Publishers: Gainesville, FL 1992. The metatellurate anion has a chemical shift around 610 ppm when analyzed using 125Te NMR at 25 °C at a frequency of 94.735 MHz and referenced externally against aqueous 1.0 M telluric acid.
The tellurate suffix in the naming of inorganic compounds
Following the IUPAC Red Book(2005) some examples are:
- metatellurate ion, or tetraoxotellurate(VI) {{chem|TeO|4|2−}} is tetraoxidotellurate(2−)
- orthotellurate ion, or hexaoxotellurate(VI) {{chem|TeO|6|6−}} is hexaoxidotellurate(6−)
- octafluorotellurate(VI) ion {{chem|TeF|8|2−}} is octafluoridotellurate(2−).