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1,3-Bis(diphenylphosphino)propane

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1,3-Bis(diphenylphosphino)propane
Names
Preferred IUPAC name (Propane-1,3-diyl)bis(diphenylphosphane)
Identifiers
CAS Number
3D model (JSmol)
Abbreviations DPPP
ChEMBL
ChemSpider
ECHA InfoCard 100.027.084 Edit this at Wikidata
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C27H26P2/c1-5-14-24(15-6-1)28(25-16-7-2-8-17-25)22-13-23-29(26-18-9-3-10-19-26)27-20-11-4-12-21-27/h1-12,14-21H,13,22-23H2Key: LVEYOSJUKRVCCF-UHFFFAOYSA-N
  • InChI=1/C27H26P2/c1-5-14-24(15-6-1)28(25-16-7-2-8-17-25)22-13-23-29(26-18-9-3-10-19-26)27-20-11-4-12-21-27/h1-12,14-21H,13,22-23H2Key: LVEYOSJUKRVCCF-UHFFFAOYAP
SMILES
  • P(c1ccccc1)(c2ccccc2)CCCP(c3ccccc3)c4ccccc4
  • c1ccc(cc1)P(CCCP(c2ccccc2)c3ccccc3)c4ccccc4
Properties
Chemical formula C27H26P2
Molar mass 412.453 g·mol
Appearance white solid
Solubility in water chlorocarbons
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

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 + Cl(CH2)3Cl → 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 BuLi → Li(CH2)3Li + 2 BuBr
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°. 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. Dppp is also used as a ligand for palladium(II) catalysts to co-polymerize carbon monoxide and ethylene to give polyketones. Dppp can sometimes be used in palladium-catalyzed arylation under Heck reaction conditions to control regioselectivity.

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): 1099–1118. 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; Collected Volumes, vol. 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. ISBN 9781118633892.
  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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