Tris(4-fluorophenyl)phosphine 98%Min White to off-white crystalline solid RC00092

Manufacturer: Hangzhou Royalchem Co.,LTD.

Website:  www.cnroyalchem.com

Tris(4-fluorophenyl)phosphine (CAS 18437-78-0)  

1. Chemical Identification  

CAS Number:  18437-78-0

EC Number:  605-885-8

Systematic Name:  Tris(4-fluorophenyl)phosphane

Synonyms:  

Phosphine, tris(p-fluorophenyl)-

 Tris(p-fluorophenyl)phosphine

 P(4-F-C₆H₄)₃

1. -Fluoro triphenylphosphine

 Tri(4-fluorophenyl)phosphine

Phosphorus tris(4-fluorophenyl)

Molecular Formula:  C₁₈H₁₂F₃P

Molecular Weight:  316.26 g/mol

1. Physical and Chemical Properties

Appearance:  Typically a white to off-white crystalline solid.

Melting Point:  ~104-108 °C (literature range).

Boiling Point:  Decomposes before boiling.

  Solubility: Soluble in common organic solvents such as dichloromethane (DCM), chloroform, tetrahydrofuran (THF), toluene, benzene, and diethyl ether.

Insoluble in water.

Density:  Not typically specified, but similar to related triarylphosphines.

Refractive Index:  Not typically a key specification.

Flash Point:   Not readily available, but combustible organic solid.

Stability:   Air and Moisture Sensitive.  

Readily oxidizes in air to the corresponding phosphine oxide. Must be stored and handled under an inert atmosphere (Argon or Nitrogen). Light sensitive.

1. Structural Information 

Structure:  A tertiary phosphine where the phosphorus atom is bonded to three 4-fluorophenyl groups (p-fluorophenyl groups). The fluorine atoms are in the para position relative to the phosphorus attachment point on each benzene ring.

Chemical Class:  Fluorinated triarylphosphine.

1. Handling and Safety (GHS Classification - Typical) 

GHS Hazard Statements:   * H315: Causes skin irritation. * H319: Causes serious eye irritation. * H335: May cause respiratory irritation. * H412: Harmful to aquatic life with long lasting effects. (Often classified based on structural analogy). * Safety Precautions: * P261: Avoid breathing dust/fume/gas/mist/vapours/spray. * P264: Wash hands thoroughly after handling. * P271: Use only outdoors or in a well-ventilated area. * P273: Avoid release to the environment. * P280: Wear protective gloves/protective clothing/eye protection/face protection. * P302+P352: IF ON SKIN: Wash with plenty of soap and water. * P305+P351+P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. * P312: Call a POISON CENTER or doctor/physician if you feel unwell. * P337+P313: If eye irritation persists: Get medical advice/attention. * P501: Dispose of contents/container to an approved waste disposal plant.

Storage:  Store in a cool, dry place. Keep container tightly sealed under an inert atmosphere (Nitrogen or Argon). Protect from light and moisture. Store away from oxidizing agents.

5. Synthesis 

Primarily synthesized via nickel-catalyzed cross-coupling of fluorobenzene with phosphorus trichloride (PCl₃):

3 4-F-C₆H₄Br + PCl₃ + 3 Mg → (4-F-C₆H₄)₃P + 3 MgBrCl

Alternatively, by reacting 4-fluorophenyllithium or 4-fluorophenylmagnesium bromide with PCl₃. * Purification often involves recrystallization under inert conditions.

6. Key Applications 

Ligand in Transition Metal Catalysis:  Its primary use is as a ligand for transition metals (especially Palladium, Platinum, Nickel, Rhodium), forming active catalysts for various organic transformations. Key reactions include: *  Suzuki-Miyaura Cross-Coupling:  (Crucial for biaryl synthesis in pharmaceuticals and materials). *  Heck Reaction.  *  Sonogashira Coupling.  *  Buchwald-Hartwig Amination.  *  Hydrogenation.  *  Hydroformylation.  *  Precursor:  Used in the synthesis of other phosphine ligands (e.g., phosphonium salts) and organophosphorus compounds. *  Stoichiometric Reagent:  Can act as a reducing agent or nucleophile in certain reactions.

7. Advantages in Catalysis (vs. Triphenylphosphine)  

The electron-withdrawing fluorine substituents make this phosphine significantly  less basic  and  more π-acidic  than triphenylphosphine (PPh₃). * This enhanced π-acidity can lead to: * Stronger metal-ligand bonds. * Increased stability of the metal complexes formed. * Modified catalytic activity and selectivity (often enhanced) in specific reactions, particularly where oxidative addition is rate-limiting (e.g., Suzuki coupling with certain substrates). * Potential for better solubility in certain reaction media compared to PPh₃.

8. Important Notes  

Air Sensitivity:   THIS IS CRITICAL.  The compound readily oxidizes upon exposure to air, forming Tris(4-fluorophenyl)phosphine Oxide (CAS 18437-77-9), which is inactive as a ligand. Handling  must  be done under an inert atmosphere (glove box or Schlenk line techniques). *  Source:  Always source from reputable chemical suppliers and confirm purity and handling instructions. *  Applications:  Primarily for research and development, particularly in organic synthesis, pharmaceuticals, agrochemicals, and materials science.