Tetrakis(triphenylphosphine)platinum(0)

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Tetrakis(triphenylphosphine)­platinum(0)
Tetrakis(triphenylphosphine)platinum(0)-3D-sticks.png
Names
IUPAC name
Tetrakis(triphenylphosphane)platinum(0)
Other names
Tetrakis(triphenylphosphane)platinum(0)
TPP platinum(0)
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.034.610 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 238-087-4
PubChem CID
  • InChI=1S/4C18H15P.Pt/c4*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;/h4*1-15H;
    Key: SYKXNRFLNZUGAJ-UHFFFAOYSA-N
  • c0ccccc0[P+](c0ccccc0)(c0ccccc0)[Pt-4]([P+](c0ccccc0)(c0ccccc0)c0ccccc0)([P+](c0ccccc0)(c0ccccc0)c0ccccc0)[P+](c0ccccc0)(c0ccccc0)c0ccccc0
Properties
C72H60P4Pt
Molar mass 1244.251 g·mol−1
Appearanceyellow 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
Occupational safety and health (OHS/OSH):
Main hazards
PPh3 is an irritant
GHS labelling: [1]
GHS-pictogram-exclam.svg
Warning
H302
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability (yellow): no hazard codeSpecial hazards (white): no code
2
1
Safety data sheet (SDS) External MSDS
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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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. [2] [3]

Contents

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. [4] 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 + Cl2cis-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"

Related Research Articles

Benzonitrile is the chemical compound with the formula C6H5(CN), abbreviated PhCN. This aromatic organic compound is a colorless liquid with a sweet bitter almond odour. It is mainly used as a precursor to the resin benzoguanamine.

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

Nickel(II) chloride (or just nickel chloride) is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

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

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

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

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic solids featuring octahedral Rh(III) centres. Depending on the value of n, the material is either a dense brown solid or a soluble reddish salt. The soluble trihydrated (n = 3) salt is widely used to prepare compounds used in homogeneous catalysis, notably for the industrial production of acetic acid and hydroformylation.

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

Palladium(II) chloride, also known as palladium dichloride and palladous chloride, are the chemical compounds with the formula PdCl2. PdCl2 is a common starting material in palladium chemistry – palladium-based catalysts are of particular value in organic synthesis. It is prepared by the reaction of chlorine with palladium metal at high temperatures.

<span class="mw-page-title-main">Tetrakis(triphenylphosphine)palladium(0)</span> Chemical compound

Tetrakis(triphenylphosphine)palladium(0) (sometimes called quatrotriphenylphosphine palladium) is the chemical compound [Pd(P(C6H5)3)4], often abbreviated Pd(PPh3)4, or rarely PdP4. It is a bright yellow crystalline solid that becomes brown upon decomposition in air.

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

Ruthenium(III) chloride is the chemical compound with the formula RuCl3. "Ruthenium(III) chloride" more commonly refers to the hydrate RuCl3·xH2O. Both the anhydrous and hydrated species are dark brown or black solids. The hydrate, with a varying proportion of water of crystallization, often approximating to a trihydrate, is a commonly used starting material in ruthenium chemistry.

<span class="mw-page-title-main">Dicarbonyltris(triphenylphosphine)ruthenium(0)</span> Chemical compound

Dicarbonyltris(triphenylphosphine)ruthenium(0) or Roper's complex is a ruthenium metal carbonyl. In it, two carbon monoxide ligands and three triphenylphosphine ligands are coordinated to a central ruthenium(0) center.

Cycloocta-1,5-diene is a cyclic hydrocarbon with the chemical formula C8H12, specifically [−(CH2)2−CH=CH−]2.

<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">Zeise's salt</span> Chemical compound

Zeise's salt, potassium trichloro(ethylene)platinate(II) hydrate, is the chemical compound with the formula K[PtCl3(C2H4)]·H2O. The anion of this air-stable, yellow, coordination complex contains an η2-ethylene ligand. The anion features a platinum atom with a square planar geometry. The salt is of historical importance in the area of organometallic chemistry as one of the first examples of a transition metal alkene complex and is named for its discoverer, William Christopher Zeise.

<span class="mw-page-title-main">Potassium tetrachloroplatinate</span> Chemical compound

Potassium tetrachloroplatinate(II) is the chemical compound with the formula K2PtCl4. This reddish orange salt is an important reagent for the preparation of other coordination complexes of platinum. It consists of potassium cations and the square planar dianion PtCl42−. Related salts are also known including Na2PtCl4, which is brown-colored and soluble in alcohols, and quaternary ammonium salts, which are soluble in a broader range of organic solvents.

Dioxygen complexes are coordination compounds that contain O2 as a ligand. The study of these compounds is inspired by oxygen-carrying proteins such as myoglobin, hemoglobin, hemerythrin, and hemocyanin. Several transition metals form complexes with O2, and many of these complexes form reversibly. The binding of O2 is the first step in many important phenomena, such as cellular respiration, corrosion, and industrial chemistry. The first synthetic oxygen complex was demonstrated in 1938 with cobalt(II) complex reversibly bound O2.

<span class="mw-page-title-main">Bis(triphenylphosphine)palladium chloride</span> Chemical compound

Bis(triphenylphosphine)palladium chloride is a coordination compound of palladium containing two triphenylphosphine and two chloride ligands. It is a yellow solid that is soluble in some organic solvents. It is used for palladium-catalyzed coupling reactions, e.g. the Sonogashira–Hagihara reaction. The complex is square planar. Many analogous complexes are known with different phosphine ligands.

Organoplatinum chemistry is the chemistry of organometallic compounds containing a carbon to platinum chemical bond, and the study of platinum as a catalyst in organic reactions. Organoplatinum compounds exist in oxidation state 0 to IV, with oxidation state II most abundant. The general order in bond strength is Pt-C (sp) > Pt-O > Pt-N > Pt-C (sp3). Organoplatinum and organopalladium chemistry are similar, but organoplatinum compounds are more stable and therefore less useful as catalysts.

<span class="mw-page-title-main">Dichlorotris(triphenylphosphine)ruthenium(II)</span> Chemical compound

Dichlorotris(triphenylphosphine)ruthenium(II) is a coordination complex of ruthenium. It is a chocolate brown solid that is soluble in organic solvents such as benzene. The compound is used as a precursor to other complexes including those used in homogeneous catalysis.

<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">Metal-phosphine complex</span>

A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).

<span class="mw-page-title-main">Bis(triphenylphosphine)platinum chloride</span> Chemical compound

Bis(triphenylphosphine)platinum chloride is a metal phosphine complex with the formula PtCl2[P(C6H5)3]2. Cis- and trans isomers are known. The cis isomer is a white crystalline powder, while the trans isomer is yellow. Both isomers are square planar about the central platinum atom. The cis isomer is used primarily as a reagent for the synthesis of other platinum compounds.

In organometallic chemistry, a transition metal alkyne complex is a coordination compound containing one or more alkyne ligands. Such compounds are intermediates in many catalytic reactions that convert alkynes to other organic products, e.g. hydrogenation and trimerization.

References

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