1,3-Bis(diphenylphosphino)propane

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1,3-Bis(diphenylphosphino)propane
Dppp.png
Dppp-from-xtal-2005-3D-balls.png
Names
IUPAC name
Propane-1,3-diylbis(diphenylphosphane)
Identifiers
3D model (JSmol)
Abbreviations DPPP
ChEMBL
ChemSpider
ECHA InfoCard 100.027.084
Properties
C27H26P2
Molar mass 412.45 g·mol−1
Appearance white solid
chlorocarbons
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

1,3-Bis(diphenylphosphino)propane (dppp) is an organophosphorus compound with the formula Ph2P(CH2)3PPh2. The compound is a white solid that is soluble in organic solvents. It is slightly air-sensitive, degrading in air to the phosphine oxide, it is classified as a diphosphine ligand in coordination chemistry and homogeneous catalysis.

The diphosphine can be prepared by the reaction of lithium diphenylphosphide and 1,3-dichloropropane (Ph = C6H5):

2 Ph2PLi + C3H6Cl2 → Ph2P(CH2)3PPh2 + 2 LiCl

However, it can be synthesised via a much more controllable (and cheaper) route, via metal-halogen exchange and then metathesis:

Br(CH2)3Br + 2 tBuLi → Li(CH2)3Li + 2 tBuBr
Li(CH2)3Li + 2 PCl3 → Cl2P(CH2)3PCl2 + 2 LiCl
Cl2P(CH2)3PCl2 + 4 PhLi → Ph2P(CH2)3PPh2 + 4 LiCl

Coordination chemistry and use as co-catalyst[edit]

The diphosphine serves as a bidentate ligand forming six-membered C3P2M chelate ring. For example, the complex dichloro(1,3-bis(diphenylphosphino)propane)nickel is prepared by combining equimolar portions of the ligand and nickel(II) chloride hexahydrate. This nickel complex serves as a catalyst for the Kumada coupling reaction.[1] Dppp is also used as a ligand for palladium(II) catalysts to co-polymerize carbon monoxide and ethylene to give polyketones.[2] Dppp can sometimes be used in palladium-catalyzed arylation under Heck reaction conditions to control regioselectivity.[3]

References[edit]

  1. ^ Kumada, Makota; Tamao, Kohei; Sumitani, Koji (1988). "Phosphine-Nickel Complex Catalyzed Cross-Coupling of Grignard Reagents with Aryl and Alkenyl Halides: 1,2-dibutylbenzene". Organic Syntheses. ; Collective Volume, 6, p. 407 
  2. ^ Drent, E.; Mul, W. P.; Smaardijk, A. A. (2001). "Polyketones". Encyclopedia Of Polymer Science and Technology. doi:10.1002/0471440264.pst273. 
  3. ^ Cabri, Walter; Candiani, Ilaria; Bedeschi Angelo; Penco, Sergio"α-Regioselectivity in Palladium-Catalyzed Arylation of Acyclic Enol Ethers" journal= Journal of Organic Chemistry, 1991, volume 57, p. 1481. doi:10.1021/jo00031a029