64345-29-5

Basic information

• Product Name: Pd2Cl2(μ-bis(diphenylphosphino)methane)2
• Synonyms: Pd2Cl2(μ-bis(diphenylphosphino)methane)2
• CAS NO: 64345-29-5
• Molecular Weight: 1052.54
• Mol File: 64345-29-5.mol
• Article Data: 15

Chemical Properties

• CAS DataBase Reference: Pd2Cl2(μ-bis(diphenylphosphino)methane)2(CAS DataBase Reference)
• NIST Chemistry Reference: Pd2Cl2(μ-bis(diphenylphosphino)methane)2(64345-29-5)
• EPA Substance Registry System: Pd2Cl2(μ-bis(diphenylphosphino)methane)2(64345-29-5)

Safety Data

• Hazardous Substances Data: 64345-29-5(Hazardous Substances Data)

Upstream product

• 603-35-0 triphenylphosphine 
• 38425-01-3 (bis(diphenylphosphino)methane)palladium(II) dichloride 
• 52522-40-4 tris(dibenzylideneacetone)dipalladium⁽⁰⁾ * CHCl₃ 
• 2071-20-7 bis-diphenylphosphinomethane 
• 15617-18-2 bis(benzonitrile)palladium(II) dichloride 
• 14221-01-3 tetrakis(triphenylphosphine) palladium⁽⁰⁾ 
• 109709-52-6 (Pd₂Cl₂((C₆H₅)2PCH₂P(C₆H₅)2)2(HCCH)) 
• 109709-51-5 (Pd₂Cl₂((C₆H₅)2PCH₂P(C₆H₅)2)2(HCCC₆H₄CH₃)) 
• 75-77-4 chloro-trimethyl-silane 
• 75-78-5 dimethylsilicon dichloride 
• 33872-80-9 o-tolyl magnesium chloride 
• 937-14-4 3-chloro-benzenecarboperoxoic acid 
• 110981-65-2 ClFe(CO)2((C₆H₅)2PCH₂P(C₆H₅)2)2PdCl 
• 612-62-4 2-Chloroquinoline 

Downstream Products

• 78274-94-9 [Pd2Cl2(.mu-CH2)(μ-bis(diphenylphosphino)methane)2] 
• 115290-49-8 Pd2(CH3)2(μ-dppm)2 
• 98194-66-2 Pd2CH3(Cl)(μ-dppm)2 
• 115290-48-7 {Pd2(μ-Cl)H(CH3)(μ-dppm)2}BPh4*3CH2Cl2 
• 52843-17-1 {(iron(carbonyl)4)2(μ-dppm)} 
• 64345-32-0 {(palladium)2(Cl)2(μ-carbonyl)(μ-dppm)2 
• 111026-17-6 {(iron(carbonyl)(nitrosyl)2)2(μ-dppm)} 
• 111026-19-8 {(palladium)2(μ3-carbonyl)2(iron)2(carbonyl)3(nitrosyl)2(μ-dppm)2 
• 98194-67-3 Pd2(CH3)2(Cl)2(μdppm)2 
• 38425-01-3 (bis(diphenylphosphino)methane)palladium(II) dichloride 
• 16743-46-7 tetracarbonyl-bis(diphenylphosphino)methane-chromium(0) 
• 16924-36-0 N(CH₂CH₃)4⁽¹⁺⁾*[Cr₂(H)(CO)10]^(1-)=N(CH₂CH₃)4[Cr₂(H)(CO)10] 
• 86028-11-7 {(palladium)2(manganese)2(carbonyl)8(μ3-carbonyl)(μ-dppm)2} 
• 10170-69-1 dimanganese decacarbonyl 

Relevant articles and documents

General route to halide-bridged organopalladium A-frame complexes and studies of reductive elimination from these bimetallic systems

Reactions of [Pd2Cl2(μ-dppm)2] with RMgX (R = Me, Et, Bu, Ph, C6H4Me-4) at low temperature, followed by addition of CBr4 and excess NH4PF6 or 1 equiv of TIPF6, provided halide-bridged organopalladium A-frame complexes of the form [Pd2R2(μ-X)(μ-dppm)2]PF6. Mixed metal complexes were obtained similarly starting from [PdCtCl2(μ-dppm)2]. Unsymmetrical A-frames of the type [Pd2(C6H2Me3-2,4,6)R(μ-Cl)(μ-d ppm)2]+ were generated reaction of [Pd(C6H2Me3-2,4,6) (dppm)2]+ (obtained by treatment of [PdCl2 (cod)] w mesitylmagnesium bromide at low temperature, followed by 2 equiv of dppm) with [Pd2R2(μ-Cl)2 (AsPh3)2]. The organopalladium A-frames did not react readily with CO, but the corresponding acyl derivatives [Pd2(COR)2(μ-Cl)(μ-dppm)2]PF6 were produced by carbonylation of [Pd2R2(μ-Cl)2(AsPh3)2] followed by addition of dppm (R = Me, Et, Bn). Thermal decomposition of [Pd2(CH2Ph)2(μ-Cl)(μ-dppm)2]Cl was found to be first order in A-frame and resulted in quantitative formation of [Pd2Cl2(μ-dppm)2] and 1,2-diphenylethane. The methyl and aryl complexes underwent both reductive elimination and hydrogen abstraction reactions. [Pd2Et2(μ-Br)(μ-ddpm)2]PF6 decomposed by β-hydride elimination and subsequent reductive elimination to yield ethene and ethane, whereas the butyl derivative gave both 1- and 2-butene. Acetic acid was formed when [Pd2(COMe)2(μ-Cl)(μ-dppm)2]PF6 was heated in dmso-d6 solution, but decarbonylation was the predominant process in dioxane. The molecular structures of [Pd2(CH2Ph)2(μ-Br)(μ-dppm)2] PF6·H2O, 2C6H6 and [Pd2Cl2(μ-Cl)(μ-dppm)2]OH· 0.5(CH3)2CO are also described.

Reactions of [PdX2(dppm)] complexes with grignard reagents

Reactions of [PdX2(dppm)] (X = Cl, Br) with a range of Grignard reagents have been investigated. Diorganopalladium complexes of the type [PdR2(dppm)] were obtained in good yield with the bulky mesityl or trimethylsilylmethyl groups,

Di(phosphine)-bridged complexes of palladium. Parahydrogen-induced polarization in hydrogenation reactions and structure determination of tris(μ-bis(diphenylphosphino)methane)dipalladium, Pd2(dppm)3

Reduction of Pd2Cl2(dppm)2 (dppm = bis(diphenylphosphino)methane) with excess NaBH4 produces a dark purple solid, I, which shows a reaction chemistry consistent with the stoichiometry Pd2Hx(dppm)2. Reaction of I with excess dppm produces the known compound Pd2(dppm)3. Crystals of Pd2(dppm)3 are monoclinic in space group P21/c with cell dimensions a = 14.733 (5) ?, b = 14.760 (5) ?, c = 29.720 (6) ?, and β = 97.44 (1)°. The structure of Pd2(dppm)3 is similar to that of the structurally characterized Pt2(dppm)3 analogue with approximate C3h symmetry. A total of 1 equiv of H2 and 1 equiv of methane is evolved per 3 Pd(dppm) units when I is treated with aqueous HCl and methyl iodide, respectively. The corresponding metal-containing products are Pd2Cl2(dppm)2 and a mixture of [Pd2I(CH3)(dppm)2]I and PdI2(dppm). The latter compound is also obtained upon oxidation of I with I2. Reaction of I with CH2I2 in dichloromethane yields a mixture of Pd2I2(μ-CH2)(dppm)2 and Pd2Cl2(μ-CH2)(dppm)2, while reaction with either Me3SiCl or Me2SiCl2 produces Pd2Cl2(dppm)2. Complex I is active in the catalytic hydrogenation of alkenes and alkynes. Parahydrogen-induced polarization (PHIP) is observed in the styrene product when solutions of I and phenylacetylene in CDCl3 are stored at -196°C under 3-4 atm of H2 for >8 h prior to reaction at 60-70°C. Similar results are obtained when para-enriched H2 is used without the storage time. Complex I decomposes upon heating in CDCl3 to mixtures of Pd2Cl2(dppm)2, PdCl2(dppm), and an unidentified red palladium compound. While this mixture is also active in hydrogenation and gives rise to PHIP, Pd2Cl2(dppm)2 by itself gives weak polarization under hydrogenation conditions and PdCl2(dppm) gives no polarization.