Tetrakis(triphenylphosphine)platinum(0)

Tetrakis(triphenylphosphine)platinum(0) is the chemical compound with the formula Pt(P(C6H5)3)4, often abbreviated Pt(PPh3)4. The bright yellow compound is used as a precursor to other platinum complexes.[1][2]

Tetrakis(triphenylphosphine)platinum(0)
Names
IUPAC name
Tetrakis(triphenylphosphane)platinum(0)
Other names
Tetrakis(triphenylphosphane)platinum(0)
TPP platinum(0)
Identifiers
3D model (JSmol)
ECHA InfoCard 100.034.610
RTECS number
  • Unregistered
Properties
C72H60P4Pt
Molar mass 1244.24 g/mol
Appearance yellow crystals
Melting point 160 °C (320 °F; 433 K)
Insoluble
Structure
four triphenylphosphine unidentate
ligands attached to a central Pt(0)
atom in a tetrahedral geometry
tetrahedral
0 D
Hazards
Main hazards PPh3 is an irritant
Safety data sheet External MSDS
R-phrases (outdated) n/a
S-phrases (outdated) S24/25
NFPA 704 (fire diamond)
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilHealth code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformReactivity (yellow): no hazard codeSpecial hazards (white): no code
1
2
Related compounds
Related complexes
 Tetrakis(triphenylphosphine)palladium(0)
tetrakis(triphenylphosphine)nickel(0)
tris(triphenylphosphine)platinum(0)
Related compounds
 triphenylphosphine
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Structure and behavior

The molecule is tetrahedral, with point group symmetry of Td, as expected for a four-coordinate metal complex of a metal with the d10 configuration.[3] Even though this complex follows the 18 electron rule, it dissociates triphenylphosphine in solution to give the 16e− derivative containing only three PPh3 ligands:

Pt(PPh3)4 → Pt(PPh3)3 + PPh3

Synthesis and reactions

The complex is typically prepared in one-pot reaction from potassium tetrachloroplatinate(II). Reduction of this platinum(II) species with alkaline ethanol in the presence of excess triphenylphosphine affords the product as a precipitate. The reaction occurs in two distinct steps. In the first step, PtCl2(PPh3)2 is generated. In the second step, this platinum(II) complex is reduced. The overall synthesis can be summarized as:

K2[PtCl4] + 2KOH + 4PPh3 + C2H5OH → Pt(PPh3)4 + 4KCl + CH3CHO + 2H2O

Pt(PPh3)4 reacts with oxidants to give platinum(II) derivatives:

Pt(PPh3)4 + Cl2 → cis-PtCl2(PPh3)2 + 2 PPh3

Mineral acids give the corresponding hydride complexes:

Pt(PPh3)4 + HCl → trans-PtCl(H)(PPh3)2 + 2 PPh3

The reaction with oxygen affords a dioxygen complex:

Pt(PPh3)4 + O2 → Pt(η2-O2)(PPh3)2 + 2 PPh3

This complex is a precursor to the ethylene complex

Pt(η2-O2)(PPh3)2 + C2H4 → Pt(η2-C2H4)(PPh3)2 + "NaBH2(OH)2"

References
  1. Ugo, R.; Cariati, F.; La Monica, G. (1990). "Tris- and tetrakis(triphenylphosphine)platinum(0)". Inorganic Syntheses. 28: 123–126. doi:10.1002/9780470132593.ch33. ISBN 9780470132593.
  2. Safety Data Sheet http://www.alfa.com/content/msds/english/10549.pdf
  3. Miessler, Gary L., and Donald A. Tarr. Inorganic Chemistry. 3rd ed. Upper Saddle River, NJ: Pearson Prentice Hall, 2004.
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