Platinum(IV) chloride

Names
IUPAC name

Platinum tetrachloride

Other names

Platinum(IV) chloride

Identifiers

CAS Number

* 13454-96-1 Y

3D model (JSmol)

* ionic monomer: Interactive image
* coordination monomer: Interactive image
* coordination polymer: Interactive image

ChemSpider |

* 19957150

EC Number |

* 236-645-1

PubChem CID

* 26031

RTECS number |

* TP2275500

UNII |

* W3YUG71TU2 Y

InChI

* InChI=1/4ClH.2Pt/h4*1H;;/q;;;;2*+2/p-4

Key: KBPRWZWTZAMEIF-XBHQNQODAX

SMILES

* 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

Chemical formula

| PtCl4
Molar mass | 336.89 g/mol
Appearance  | brown-red powder
Density | 4.303 g/cm3 (anhydrous)
2.43 g/cm3 (pentahydrate)
Melting point |  370 °C (698 °F; 643 K) (decomposes)

Solubility in water

| 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

Magnetic susceptibility (χ)

| −93.0·10−6 cm3/mol
Structure

Molecular shape

| Square planar
Hazards
GHS pictograms |
GHS Signal word | Danger

GHS hazard statements

| H290, H301, H314, H317, H334

GHS precautionary statements

| P234, P260, P261, P264, P270, P272, P280, P285, P301+310, P301+330+331, P302+352, P303+361+353, P304+340, P304+341, P305+351+338, P310, P321, P330, P333+313, P342+311, P363, P390, P404, P405, P501
Lethal dose or concentration (LD, LC):

LD50 (median dose)

| 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).

Infobox references

Tracking categories (test):

* SizeSet

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.

## 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]

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.

## References

* Cotton, S. A. Chemistry of Precious Metals, Chapman and Hall (London): 1997. ISBN 0-7514-0413-6.

1. ↑ "Platinum tetrachloride" (in en). https://pubchem.ncbi.nlm.nih.gov/compound/26031#section=Safety-and-Hazards.
2. ↑ M. F. Pilbrow (1972). "Crystal structure of platinum tetrachloride" (in en). 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" (in en). 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. https://books.google.com/books?id=n6A9AAAAIAAJ.
6. ↑ Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4.

* v
* t
* e

Platinum compounds

Pt(0)|

* Pt(P(C6H5)3)4

Pt(II)|

* Pt(NH3)2(CO2)2C4H6
* cis-Pt(NH3)2Cl2
* trans-Pt(NH3)2Cl2
* K2Pt(CN)4
* Pt(NH3)4PtCl4
* Pt(NH3)2CO2CH2O
* C6H10(NH2)2PtC2O4
* NH3PtCl2NC5H4CH3
* Pt(C2H3O2)2
* PtBr2
* PtCl2
* K2PtCl4
* (PtCl(NH3)2C6H12(NH2)2)Pt(NH3)2(NO3)4
* Pt(OH)2
* PtS

| Organoplatinum(II) compounds|

* PtCl2C8H12
* KPtCl3C2H4

|

Pt(IV)|

* PtO2
* (NH4)2PtCl6
* H2PtCl6
* PtBr4
* PtCl4
* PtF4
* K2PtCl6
* Pt(C2H3O2)2Cl2NH3NH2C6H11
* Na2PtCl6
* Pt(OH)4
* PtS2
* PtSe2
* XeFPtF5

Pt(V)|

* PtF5
* O2PtF6
* XePtF6

Pt(VI)|

* PtF6

* v
* t
* e

Salts and covalent derivatives of the chloride ion

HCl |  |  |  | He

|
|
|
|

LiCl | BeCl2 | BCl3
B2Cl4 | CCl4 | NCl3
ClN3 | Cl2O
ClO2
Cl2O7 | ClF
ClF3
ClF5 | Ne
NaCl | MgCl2 | AlCl
AlCl3 | SiCl4 | P2Cl4
PCl3
PCl5 | S2Cl2
SCl2
SCl4 | Cl2 | Ar
KCl | CaCl
CaCl2 | ScCl3 | TiCl2
TiCl3
TiCl4 | VCl2
VCl3
VCl4
VCl5 | CrCl2
CrCl3
CrCl4 | MnCl2 | FeCl2
FeCl3 | CoCl2
CoCl3 | NiCl2 | CuCl
CuCl2 | ZnCl2 | GaCl2
GaCl3 | GeCl2
GeCl4 | AsCl3
AsCl5 | Se2Cl2
SeCl4 | BrCl | KrCl
RbCl | SrCl2 | YCl3 | ZrCl3
ZrCl4 | NbCl4
NbCl5 | MoCl2
MoCl3
MoCl4
MoCl5
MoCl6 | TcCl4 | RuCl3 | RhCl3 | PdCl2 | AgCl | CdCl2 | InCl
InCl2
InCl3 | SnCl2
SnCl4 | SbCl3
SbCl5 | Te3Cl2
TeCl4 | ICl
ICl3 | XeCl
XeCl2
CsCl | BaCl2 |  | HfCl4 | TaCl5 | WCl2
WCl3
WCl4
WCl5
WCl6 | Re3Cl9
ReCl4
ReCl5
ReCl6 | OsCl4 | IrCl2
IrCl3
IrCl4 | PtCl2
PtCl4 | AuCl
AuCl3 | Hg2Cl2,
HgCl2 | TlCl | PbCl2,
PbCl4 | BiCl3 | PoCl2,
PoCl4 | AtCl  | RnCl2
FrCl | RaCl2 |  | Rf  | Db  | Sg  | Bh  | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og
| ↓  |  |
LaCl3 | CeCl3 | PrCl3 | NdCl2,
NdCl3 | PmCl3 | SmCl2,
SmCl3 | EuCl2,
EuCl3 | GdCl3 | TbCl3 | DyCl2,
DyCl3 | HoCl3 | ErCl3 | TmCl2
TmCl3 | YbCl2
YbCl3 | LuCl3
AcCl3 | ThCl4 | PaCl5 | UCl3
UCl4
UCl5
UCl6 | NpCl4 | PuCl3 | AmCl2
AmCl3 | CmCl3 | BkCl3 | CfCl3 | EsCl3 | Fm  | Md  | No  | LrCl3

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*[CID]: Compound ID
*[H290]: May be corrosive to metals
*[H301]: Toxic if swallowed
*[H314]: Causes severe skin burns and eye damage
*[H317]: May cause an allergic skin reaction
*[H334]: May cause allergy or asthma symptoms of breathing difficulties if inhaled
*[P234]: Keep only in original container
*[P260]: Do not breathe dust/fume/gas/mist/vapours/spray
*[P261]: Avoid breathing dust/fume/gas/mist/vapours/spray
*[P264]: Wash … thoroughly after handling
*[P270]: Do not eat, drink or smoke when using this product
*[P272]: Contaminated work clothing should not be allowed out of the workplace
*[P280]: Wear protective gloves/protective clothing/eye protection/face protection
*[P285]: In case of inadequate ventilation wear respiratory protection
*[P301+310]: IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician
*[P301+330+331]: IF SWALLOWED: Rinse mouth. Do NOT induce vomiting
*[P302+352]: IF ON SKIN: Wash with soap and water
*[P303+361+353]: IF ON SKIN (or hair): Remove/Take off immediately all contaminated clothing. Rinse skin with water/shower
*[P304+340]: IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing
*[P304+341]: IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing
*[P305+351+338]: IF IN EYES: Rinse continuously with water for several minutes. Remove contact lenses if present and easy to do – continue rinsing
*[P310]: Immediately call a POISON CENTER or doctor/physician
*[P321]: Specific treatment (see … on this label)
*[P330]: Rinse mouth
*[P333+313]: If skin irritation or a rash occurs: Get medical advice/attention
*[P342+311]: Call a POISON CENTER or doctor/physician
*[P363]: Wash contaminated clothing before reuse
*[P390]: Absorb spillage to prevent material damage
*[P404]: Store in a closed container
*[P405]: Store locked up
*[P501]: Dispose of contents/container to …
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