Thallium(III) nitrate

Thallium(III) nitrate

Names
IUPAC name thallium(III) trinitrate
Other names thallic nitrate
Identifiers
CAS Number	13746-98-0  Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:229458
ChemSpider	140409  N
ECHA InfoCard	100.033.918
PubChem CID	159690
UNII	810U72316M  Y
UN number	2727
CompTox Dashboard (EPA)	DTXSID50890716
InChI InChI=1S/3NO3.Tl/c3*2-1(3)4;/q3*-1;+3 N Key: KLBIUKJOZFWCLW-UHFFFAOYSA-N N
SMILES [Tl+3].O=[N+]([O-])[O-].[O-][N+]([O-])=O.[O-][N+]([O-])=O
Properties
Chemical formula	Tl(NO3)3
Molar mass	390.398 g/mol
Appearance	colorless solid
Density	3.36 g/cm3
Melting point	103 °C (217 °F; 376 K)
Boiling point	decomposes
Solubility in water	reacts
Structure
Crystal structure	hexagonal
Space group	R3
Lattice constant	a = 11.821 Å, c = 10.889 Å
Lattice volume (V)	1313.7 Å3
Hazards
GHS labelling:
Pictograms
Signal word	Danger
NFPA 704 (fire diamond)	4 1 0 OX
NIOSH (US health exposure limits):
IDLH (Immediate danger)	15 mg/m3
Safety data sheet (SDS)	Fisher Scientific
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N  verify  (what is  YN ?) Infobox references

Thallium(III) nitrate, also known as thallic nitrate, is a thallium compound with chemical formula Tl (NO₃)₃. ^[1] Normally found as the trihydrate, it is a colorless and highly toxic salt which hydrolyses in water to thallium(III) oxide. ^[2] 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: ^[3]

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. ^[4]

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: ^[5]

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: ^{[5] [6]}

References

1. "Material Safety Data Sheet". Thermo Fisher Scientific.
2. Norman Binsted; Andrew L Hector; William Levason (2000). "Synthesis and properties of thallium(III) periodate". Inorganica Chimica Acta. 298 (1): 116–119. doi:10.1016/S0020-1693(99)00427-2.
3. Alexander McKillop; John D. Hunt; Edward C. Taylor; Frank Kienzle (1970). "Thallium in organic synthesis. XX. Oxidative rearrangement of olefins with thallium(III) nitrate: A simple one-step synthesis of aldehydes and ketones". Tetrahedron Letters. 11 (60): 5275–5280. doi:10.1016/S0040-4039(00)99993-3.
4. R. Faggiani; I. D. Brown (1978). "Thallium(III) trinitrate trihydrate". Acta Crystallographica B. 34 (5): 1675–1676. Bibcode:1978AcCrB..34.1675F. doi:10.1107/S0567740878006305.
5. Sibi, Mukund P.; Silva, Luiz F.; Carneiro, Vânia M. T. (2008-09-15). John Wiley & Sons, Ltd (ed.). Thallium(III) Nitrate Trihydrate. Chichester, UK: John Wiley & Sons, Ltd. doi:10.1002/047084289x.rt085.pub2. ISBN   978-0-471-93623-7.
6. Hyo Jin Gim; Hua Li; So Ra Jung; Yong Joo Park; Jae-Ha Ryu; Kyu Hyuck Chung; Raok Jeon (2014). "Design and synthesis of azaisoflavone analogs as phytoestrogen mimetics". European Journal of Medicinal Chemistry. 85: 107–118. doi:10.1016/j.ejmech.2014.07.030. PMID   25078314.