Platinum(IV) chloride

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Platinum(IV) chloride
Platinum(IV) chloride.jpg
Platinum(IV)-chloride-2D.png
Names
IUPAC name
Platinum tetrachloride
Other names
Platinum(IV) chloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.300 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 236-645-1
PubChem CID
RTECS number
  • TP2275500
UNII
  • InChI=1/4ClH.2Pt/h4*1H;;/q;;;;2*+2/p-4
    Key: KBPRWZWTZAMEIF-XBHQNQODAX
  • ionic monomer:[Pt+4].[Cl-].[Cl-].[Cl-].[Cl-]
  • coordination monomer:Cl[Pt](Cl)(Cl)Cl
  • coordination polymer:Cl[Pt-]1(Cl)(Cl)(Cl)[Cl+][Pt-2]2([Cl+]1)(Cl)(Cl)[Cl+][Pt-2]1([Cl+]2)(Cl)(Cl)[Cl+][Pt-2]2([Cl+]1)(Cl)(Cl)[Cl+][Pt-2]1([Cl+]2)(Cl)(Cl)[Cl+][Pt-2]2([Cl+]1)(Cl)(Cl)[Cl+][Pt-2]1([Cl+]2)(Cl)(Cl)[Cl+][Pt-2]2([Cl+]1)(Cl)(Cl)[Cl+][Pt-2]1([Cl+]2)(Cl)(Cl)[Cl+][Pt-]([Cl+]1)(Cl)(Cl)(Cl)Cl
Properties
PtCl4
Molar mass 336.89 g/mol
Appearancebrown-red powder
Density 4.303 g/cm3 (anhydrous)
2.43 g/cm3 (pentahydrate)
Melting point 370 °C (698 °F; 643 K) (decomposes)
58.7 g/100 mL (anhydrous)
very soluble (pentahydrate)
Solubility anhydrous
soluble in acetone
slightly soluble in ethanol
insoluble in ether
pentahydrate
soluble in alcohol, ether
93.0·10−6 cm3/mol
Structure
Square planar
Hazards
GHS labelling: [1]
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg
Danger
H290, H301, H314, H317, H334
P234, P260, P261, P264, P270, P272, P280, P285, P301+P310, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P304+P341, P305+P351+P338, P310, P321, P330, P333+P313, P342+P311, P363, P390, P404, P405, P501
Lethal dose or concentration (LD, LC):
276 mg/kg (rat, oral)
Related compounds
Other anions
Platinum(IV) bromide
Platinum(IV) fluoride
Platinum(IV) sulfide
Other cations
Iridium(IV) chloride
Related compounds
Platinum(II) chloride
Platinum(VI) fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Platinum(IV) chloride is the inorganic compound of platinum and chlorine with the empirical formula PtCl4. This brown solid features platinum in the 4+ oxidation state.

Contents

Structure

Typical of Pt(IV), the metal centers adopt an octahedral coordination geometry, {PtCl6}. This geometry is achieved by forming a polymer wherein half of the chloride ligands bridge between the platinum centers. Because of its polymeric structure, PtCl4 dissolves only upon breaking the chloride bridging ligands. Thus, addition of HCl give H2PtCl6. Lewis base adducts of Pt(IV) of the type cis-PtCl4L2 are known, but most are prepared by oxidation of the Pt(II) derivatives. [2]

Platinum(IV)-chloride-CM-3D-balls.png
Part of a (PtCl4) chain from the crystal structure of platinum(IV) chloride

Formation and reactions

PtCl4 is mainly encountered in the handling of chloroplatinic acid, obtained by dissolving of Pt metal in aqua regia. Heating H2PtCl6 to 220 °C gives impure PtCl4: [3]

H2PtCl6 → PtCl4 + 2 HCl

A purer product can be produced by heating under chlorine gas at 250 °C. [4]

If excess acids are removed, PtCl4 crystallizes from aqueous solutions in large red crystals of pentahydrate PtCl4·5(H2O), [5] which can be dehydrated by heating to about 300 °C in a current of dry chlorine. The pentahydrate is stable and is used as the commercial form of PtCl4.

Treatment of PtCl4 with aqueous base gives the [Pt(OH)6]2− ion. With methyl Grignard reagents followed by partial hydrolysis, PtCl4 converts to the cuboidal cluster [Pt(CH3)3(OH)]4. [6] Upon heating PtCl4 evolves chlorine to give PtCl2:

PtCl4 → PtCl2 + Cl2

The heavier halides, PtBr4 and PtI4, are also known.

Related Research Articles

<span class="mw-page-title-main">Aqua regia</span> Mixture of nitric acid and hydrochloric acid in a 1:3 molar ratio

Aqua regia is a mixture of nitric acid and hydrochloric acid, optimally in a molar ratio of 1:3. Aqua regia is a fuming liquid. Freshly prepared aqua regia is colorless, but it turns yellow, orange or red within seconds from the formation of nitrosyl chloride and nitrogen dioxide. It was so named by alchemists because it can dissolve noble metals like gold and platinum, though not all metals.

Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated forms, which are both hygroscopic. They feature iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while all forms are mild oxidizing agents. It is used as a water cleaner and as an etchant for metals.

<span class="mw-page-title-main">Zinc chloride</span> Chemical compound

Zinc chloride is an inorganic chemical compound with the formula ZnCl2·nH2O, with n ranging from 0 to 4.5, forming hydrates. Zinc chloride, anhydrous and its hydrates, are colorless or white crystalline solids, and are highly soluble in water. Five hydrates of zinc chloride are known, as well as four forms of anhydrous zinc chloride.

<span class="mw-page-title-main">Titanium tetrachloride</span> Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4", as a phonetic representation of the symbols of its molecular formula.

<span class="mw-page-title-main">Lead(II) chloride</span> Chemical compound

Lead(II) chloride (PbCl2) is an inorganic compound which is a white solid under ambient conditions. It is poorly soluble in water. Lead(II) chloride is one of the most important lead-based reagents. It also occurs naturally in the form of the mineral cotunnite.

Tin(IV) chloride, also known as tin tetrachloride or stannic chloride, is an inorganic compound of tin and chlorine with the formula SnCl4. It is a colorless hygroscopic liquid, which fumes on contact with air. It is used as a precursor to other tin compounds. It was first discovered by Andreas Libavius (1550–1616) and was known as spiritus fumans libavii.

<span class="mw-page-title-main">Manganese(II) chloride</span> Chemical compound

Manganese(II) chloride is the dichloride salt of manganese, MnCl2. This inorganic chemical exists in the anhydrous form, as well as the dihydrate (MnCl2·2H2O) and tetrahydrate (MnCl2·4H2O), with the tetrahydrate being the most common form. Like many Mn(II) species, these salts are pink, with the paleness of the color being characteristic of transition metal complexes with high spin d5 configurations.

<span class="mw-page-title-main">Copper(II) chloride</span> Chemical compound

Copper(II) chloride, also known as cupric chloride, is an inorganic compound with the chemical formula CuCl2. The monoclinic yellowish-brown anhydrous form slowly absorbs moisture to form the orthorhombic blue-green dihydrate CuCl2·2H2O, with two water molecules of hydration. It is industrially produced for use as a co-catalyst in the Wacker process.

<span class="mw-page-title-main">Metal ammine complex</span> Class of chemical compounds

In coordination chemistry, metal ammine complexes are metal complexes containing at least one ammonia ligand. "Ammine" is spelled this way for historical reasons; in contrast, alkyl or aryl bearing ligands are spelt with a single "m". Almost all metal ions bind ammonia as a ligand, but the most prevalent examples of ammine complexes are for Cr(III), Co(III), Ni(II), Cu(II) as well as several platinum group metals.

<span class="mw-page-title-main">Hafnium tetrachloride</span> Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

<span class="mw-page-title-main">Chloroplatinic acid</span> Chemical compound

Chloroplatinic acid (also known as hexachloroplatinic acid) is an inorganic compound with the formula [H3O]2[PtCl6](H2O)x (0 ≤ x ≤ 6). A red solid, it is an important commercial source of platinum, usually as an aqueous solution. Although often written in shorthand as H2PtCl6, it is the hydronium (H3O+) salt of the hexachloroplatinate anion (PtCl2−
6
). Hexachloroplatinic acid is highly hygroscopic.

<span class="mw-page-title-main">Platinum(II) chloride</span> Chemical compound

Platinum(II) chloride is the chemical compound PtCl2. It is an important precursor used in the preparation of other platinum compounds. It exists in two crystalline forms, but the main properties are somewhat similar: dark brown, insoluble in water, diamagnetic, and odorless.

<span class="mw-page-title-main">Thorium(IV) chloride</span> Chemical compound

Thorium(IV) chloride describes a family of inorganic compounds with the formula ThCl4(H2O)n. Both the anhydrous and tetrahydrate (n = 4) forms are known. They are hygroscopic, water-soluble white salts.

Osmium compounds are compounds containing the element osmium (Os). Osmium forms compounds with oxidation states ranging from −2 to +8. The most common oxidation states are +2, +3, +4, and +8. The +8 oxidation state is notable for being the highest attained by any chemical element aside from iridium's +9 and is encountered only in xenon, ruthenium, hassium, iridium, and plutonium. The oxidation states −1 and −2 represented by the two reactive compounds Na
2
[Os
4
(CO)
13
]
and Na
2
[Os(CO)
4
]
are used in the synthesis of osmium cluster compounds.

Trirhenium nonachloride is a compound with the formula ReCl3, sometimes also written Re3Cl9. It is a dark red hygroscopic solid that is insoluble in ordinary solvents. The compound is important in the history of inorganic chemistry as an early example of a cluster compound with metal-metal bonds. It is used as a starting material for synthesis of other rhenium complexes.

<span class="mw-page-title-main">Osmium(IV) chloride</span> Chemical compound

Osmium(IV) chloride or osmium tetrachloride is the inorganic compound composed of osmium and chlorine with the empirical formula OsCl4. It exists in two polymorphs (crystalline forms). The compound is used to prepare other osmium complexes.

<span class="mw-page-title-main">Selenium tetrachloride</span> Chemical compound

Selenium tetrachloride is the inorganic compound composed with the formula SeCl4. This compound exists as yellow to white volatile solid. It is one of two commonly available selenium chlorides, the other example being selenium monochloride, Se2Cl2. SeCl4 is used in the synthesis of other selenium compounds.

<span class="mw-page-title-main">Sulfur tetrachloride</span> Chemical compound

Sulfur tetrachloride is an inorganic compound with chemical formula SCl4. It has only been obtained as an unstable pale yellow solid. The corresponding SF4 is a stable, useful reagent.

<span class="mw-page-title-main">Metal halides</span>

Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. A few metal halides are discrete molecules, such as uranium hexafluoride, but most adopt polymeric structures, such as palladium chloride.

<span class="mw-page-title-main">Lead(IV) chloride</span> Chemical compound

Lead tetrachloride, also known as lead(IV) chloride, has the molecular formula PbCl4. It is a yellow, oily liquid which is stable below 0 °C, and decomposes at 50 °C. It has a tetrahedral configuration, with lead as the central atom. The Pb–Cl covalent bonds have been measured to be 247 pm and the bond energy is 243 kJ⋅mol−1.

References

  1. "Platinum tetrachloride". pubchem.ncbi.nlm.nih.gov. Retrieved 27 December 2021.
  2. M. F. Pilbrow (1972). "Crystal structure of platinum tetrachloride". Journal of the Chemical Society, Chemical Communications (5): 270–271. doi:10.1039/C39720000270.
  3. A. E. Schweizer; G. T. Kerr (1978). "Thermal decomposition of hexachloroplatinic acid". Inorganic Chemistry. 17 (8): 2326–2327. doi:10.1021/ic50186a067.
  4. Handbuch der präparativen anorganischen Chemie. 1 (3., umgearb. Aufl ed.). Stuttgart: Enke. 1975. p. 1709. ISBN   978-3-432-02328-1.
  5. George Samuel Newth (1920). A text-book of inorganic chemistry. Longmans, Green, and co. p. 694.
  6. Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. ISBN   0-7506-3365-4.