1,3-Bis(diphenylphosphino)propane

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.

1,3-Bis(diphenylphosphino)propane
Names
IUPAC name
Propane-1,3-diylbis(diphenylphosphane)
Identifiers
3D model (JSmol)
Abbreviations DPPP
ChEMBL
ChemSpider
ECHA InfoCard 100.027.084
UNII
Properties
C27H26P2
Molar mass 412.453 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

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

The diphosphine serves as a bidentate ligand forming six-membered C3P2M chelate ring with a natural bite angle of 91°.[1] 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.[2] Dppp is also used as a ligand for palladium(II) catalysts to co-polymerize carbon monoxide and ethylene to give polyketones.[3] Dppp can sometimes be used in palladium-catalyzed arylation under Heck reaction conditions to control regioselectivity.[4]

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References
  1. Birkholz (née Gensow), Mandy-Nicole; Freixa, Zoraida; van Leeuwen, Piet W. N. M. (2009). "Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions". Chemical Society Reviews. 38 (4): 1099. doi:10.1039/B806211K. PMID 19421583.
  2. 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
  3. Drent, E.; Mul, W. P.; Smaardijk, A. A. (2001). "Polyketones". Encyclopedia Of Polymer Science and Technology. doi:10.1002/0471440264.pst273.
  4. 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
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