Thallium(III) nitrate
{{Chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 470605751
| ImageFile = Thallium nitrate.svg
| ImageSize =
| IUPACName = thallium(III) trinitrate
| OtherNames = thallic nitrate
|Section1={{Chembox Identifiers
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 13746-98-0
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 810U72316M
| UNNumber = 2727
| PubChem = 159690
| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
| ChemSpiderID = 140409
| ChEBI = 229458
| SMILES = [Tl+3].O=[N+]([O-])[O-].[O-][N+]([O-])=O.[O-][N+]([O-])=O
| StdInChI_Ref = {{stdinchicite|changed|chemspider}}
| StdInChI =1S/3NO3.Tl/c3*2-1(3)4;/q3*-1;+3
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
| StdInChIKey = KLBIUKJOZFWCLW-UHFFFAOYSA-N
}}
|Section2={{Chembox Properties
| Formula = Tl(NO3)3
| MolarMass = 390.398 g/mol
| Appearance = colorless solid
| Density = 3.36 g/cm3
| MeltingPtC = 103
| MeltingPt_notes =
| BoilingPt = decomposes
| Solubility = reacts
}}
| Section3 = {{Chembox Structure
| Structure_ref =
| CrystalStruct = hexagonal
| SpaceGroup = R{{overline|3}}
| LattConst_a = 11.821 Å
| LattConst_b =
| LattConst_c = 10.889 Å
| LattConst_alpha =
| LattConst_beta =
| LattConst_gamma =
| LattConst_ref =
| LattConst_Comment =
| UnitCellVolume = 1313.7 Å3
| UnitCellFormulas =
| Coordination =
}}
|Section4={{Chembox Hazards
| GHSPictograms = {{GHS03}}{{GHS06}}{{GHS08}}
| ExternalSDS = [https://www.fishersci.com/store/msds?partNumber=AA8799906&productDescription=THAL+III+NRATE+TRIHYD+99.5+5G&vendorId=VN00024248&countryCode=US&language=en Fisher Scientific]
| MainHazards =
| FlashPt =
| AutoignitionPt =
| NFPA-H = 4
| NFPA-R = 0
| NFPA-F = 1
| NFPA-S = OX
| IDLH = 15 mg/m3
| GHSSignalWord = Danger
}}
}}
Thallium(III) nitrate, also known as thallic nitrate, is a thallium compound with chemical formula Tl(NO3)3.{{Cite web |title=Material Safety Data Sheet |url=https://www.fishersci.ca/store/msds?partNumber=AA8799922&productDescription=thallium-iii-nitrate-trihydrate-99-5-metals-basis-3&language=en&countryCode=CA |website=Thermo Fisher Scientific}} Normally found as the trihydrate, it is a colorless and highly toxic salt which hydrolyses in water to thallium(III) oxide.{{cite journal |author1=Norman Binsted |author2=Andrew L Hector |author3=William Levason |title=Synthesis and properties of thallium(III) periodate |journal=Inorganica Chimica Acta |date=2000 |volume=298 |issue=1 |pages=116–119 |doi=10.1016/S0020-1693(99)00427-2 |language=en}} It is a strong oxidizing agent useful in organic synthesis.
Prepration
The trihydrate is prepared by dissolving thallium(III) oxide in concentrated nitric acid at 80 °C, followed by cooling of the resulting solution:{{cite journal |author1=Alexander McKillop |author2=John D. Hunt |author3=Edward C. Taylor |author4=Frank Kienzle |title=Thallium in organic synthesis. XX. Oxidative rearrangement of olefins with thallium(III) nitrate: A simple one-step synthesis of aldehydes and ketones |journal=Tetrahedron Letters |date=1970 |volume=11 |issue=60 |pages=5275–5280 |doi=10.1016/S0040-4039(00)99993-3 |language=en}}
:Tl2O3 + 6 HNO3 → 2 Tl(NO3)3 + 3 H2O
Structure
Thallium(III) nitrate trihydrate, Tl(NO3)3·3H2O, crystallizes in the hexagonal crystal system and consists of a nine-coordinate thallium center with three bidentate nitrate ligands and three monodentate water ligands.{{cite journal |author1=R. Faggiani |author2=I. D. Brown |title=Thallium(III) trinitrate trihydrate |journal=Acta Crystallographica B |date=1978 |volume=34 |issue=5 |pages=1675–1676 |doi=10.1107/S0567740878006305 |bibcode=1978AcCrB..34.1675F |language=en}}
Organic synthesis
Despite its toxicity, thallium(III) nitrate is sometimes used in the laboratory, such as in the oxidation of methoxyl phenols to quinone acetals:{{Cite book |last1=Sibi |first1=Mukund P. |url=https://onlinelibrary.wiley.com/doi/10.1002/047084289X.rt085.pub2 |title=Thallium(III) Nitrate Trihydrate |last2=Silva |first2=Luiz F. |last3=Carneiro |first3=Vânia M. T. |date=2008-09-15 |publisher=John Wiley & Sons, Ltd |isbn=978-0-471-93623-7 |editor-last=John Wiley & Sons, Ltd |location=Chichester, UK |language=en |doi=10.1002/047084289x.rt085.pub2}}
File:Thallium nitrate oxidation of methoxy phenols.png
Another use of thallium(III) nitrate is the oxidization of alkenes to acetals, cyclic alkenes to ring contracted aldehydes, and terminal alkynes to carboxylic acids. Ketones are also oxidized to carboxylic acids or esters in the presence of methanol. Illustrated below is an example of alkene oxidation to an acetal:{{cite journal |author1=Hyo Jin Gim |author2=Hua Li |author3=So Ra Jung |author4=Yong Joo Park |author5=Jae-Ha Ryu |author6=Kyu Hyuck Chung |author7=Raok Jeon |title=Design and synthesis of azaisoflavone analogs as phytoestrogen mimetics |journal=European Journal of Medicinal Chemistry |date=2014 |volume=85 |pages=107–118 |doi=10.1016/j.ejmech.2014.07.030 |pmid=25078314 |language=en}}
References
{{clear}}
{{Thallium compounds}}
{{nitrates}}
Category:Thallium(III) compounds
Category:Reagents for organic chemistry
{{inorganic-compound-stub}}