Chlorotris(triphenylphosphine)rhodium(I)

• Catalog No.: 10468
• CAS Number: 14694-95-2
• M. F.: C54H45ClP3Rh
• M. W.: 925.214883
• Purity: 97%

SYNONYMS

• Title: 三(三苯基膦)氯化铑(I)
• IUPAC name: chlororhodium; tris(triphenylphosphane)
• IUPAC Traditional name: chlororhodium; tris(triphenylphosphine)
• Synonyms: Wilkinson's catalyst; Tris(triphenylphosphine)rhodium(I) chloride

DATABASE IDS

• MDL Number: MFCD00010016
• EC Number: 238-744-5
• Merck Index: 1410047
• CAS Number: 14694-95-2

PROPERTIES

• Purity: 97%
• Apperance: Micro Crystals
• Melting Point: ca 250°C dec.
• Solubility: Soluble in most solvents (e.g. benzene, ethanol, chloroform, dichloromethane) but with phosphine dissociation. Reacts with O2 in solution
• GHS Hazard statements: H413
• GHS Precautionary statements: P273-P501A
• Risk Statements: 53
• Safety Statements: 60-61
• TSCA Listed: 是

REFERENCES

• Homogeneous hydrogenation catalyst: J. Chem. Soc.(A), 1711 (1966), useful e.g. for the selective reduction of an unhindered alkene, of an unconjugated in the presence of a conjugated alkene: Org. Synth. Coll., 6, 459 (1988), or an alkene in the presence of a nitro group: J. Org. Chem., 67, 3163 (2002). Hydroxyl groups protected as their allyl ethers may be deprotected by isomerization with Wilkinson's Catalyst to the more readily-hydrolyzed 1-propenyl ether: J. Org. Chem., 38, 3224 (1973).
• Aldehydes undergo decarbonylation with the complex: Tetrahedron Lett., 3969 (1965); J. Am. Chem. Soc., 93, 5465 (1971). The need for stoichiometric amounts of the complex, due to formation of an inactive Rh carbonyl complex, is a serious disadvantage. However, in the presence of Diphenylphosphonic azide, A12124, which regenerates the catalyst from the carbonyl complex, decarbonylations can be carried out catalytically at room temperature, providing a much more cost-effective and attractive method for this type of transformation: J. Org. Chem., 57, 5075 (1992).
• Catalyst for hydrosilylation reactions, e.g. with Triethylsilane, A10320, including ɑ?-unsaturated ketones to silyl enol ethers, which can be hydrolyzed to saturated ketones: Organometallics, 1, 1390 (1982), and ɑ?-unsaturated esters to silyl ketene acetals with high (Z)-selectivity: Synth. Commun., 17, 1 (1989).
• Co-catalyst giving improved results in intramolecular Heck coupling reactions catalyzed by Pd(OAc)₂: J. Org. Chem., 64, 3461 (1999).
• Used by Grigg for the catalytic [2+2+2] cyclotrimerization of alkynes, providing an efficient route to benzene-fused ring systems. See, e.g.: J. Chem. Soc., Perkin 1, 1357 (1988). For an intermolecular example with reaction scheme, see 1,6-Heptadiyne, A11318. Intramolecular assembly of suitably constructed triynes can also be accomplished to form benzene rings: Tetrahedron, 45, 6239 (1989). Also catalyzes the [5+2] cycloaddition of vinylcyclopropanes and alkynes: J. Am. Chem. Soc., 117, 4720 (1995); 120, 1940 (1998).
• Electron-deficient olefins undergo Rh-catalyzed 1,4-addition with Bis(pinacolato)diboron, L16088, e.g. 2-cyclohexen-1-one to the ?-borylcyclohexanone: Tetrahedron Lett., 43, 2323 (2002):