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1,3-bis(diphenylphosphino)propane]dichloro nickel(¢ò)

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Preparation

NiCl2(dppp) is prepared by combining equal molar portions of nickel(II) chloride hexahydrate with 1,3-bis(diphenylphosphino)propane in 2-propanol.[1]

Ni(H2O)6Cl2 + dppp ¡ú NiCl2(dppp) + 6 H2O
[edit]Reactions

It is used in Grignard reagent reactions involving cross-coupling of aryl halides, converting enol ethers, dithioacetals, and vinyl sulfides to olefins. NiCl2(dppp) is used because the douple phosphate ligand minimizes the reduction reactions with labile ¦Â-hydrogens. [2]

Cross-coupling reactions of R-X compounds with organometallic nucleophiles are catalyzed by transition metal complexes such as NiCl2(dppp). The R group consists of aryl, vinyl, or allyl groups and the X group is a good leaving group. Cross-coupling reactions are effective at producing carbon-carbon bonds. Catalysts that have bidentate phosphine ligands serve as the best catalysts.[3]

NiCl2(dppp) serves as the catalyst by bonding the two cross-coupling components to the nickel. The cross-coupling proceeds by oxidative addition of the aryl, vinyl, or allyl halide to NiCl2(dppp) forming an oxidative addition adduct, R1-NiCl(dppp). The organometallic nucleophile, R2-MgBr, reacts with R1-NiCl(dppp) and is followed by the cross-coupling reaction producing the R1-R2 product. [4]

The compound is a catalyst for Kumada coupling reactions involving alkyl, alkenyl, aryl, and heteroaryl Grignard reagents with aryl, heteroaryl, and alkenyl halides. [1]

[edit]References

^ a b Kumada, Makota; Tamao, Kohei; Sumitani, Koji (1988), "Phosphine-Nickel Complex Catalyzed Cross-Coupling of Grignard Reagents with Aryl and Alkenyl Halides: 1,2-dibutylbenzene", Org. Synth.; Coll. Vol. 6: 407
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