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Dichloro(1,3-bis(diphenylphosphino)propane)nickel

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Dichloronickel
Names
Systematic IUPAC name Dichloronickel
Other names 1,3-bis(diphenyl­phosphino)propanenickel(II) chloride; NiCl2(dppp)
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.132.628 Edit this at Wikidata
EC Number
  • 605-052-3
PubChem CID
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C27H26P2.2Cl.Ni/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,13,22-23H2;;;
SMILES
  • Cl1((c2ccccc2)(c3ccccc3)CCC1(c4ccccc4)c5ccccc5)Cl
Properties
Chemical formula C27H26Cl2NiP2
Molar mass 542.05 g·mol
Appearance Orange to red-orange powder
Melting point 213 °C (415 °F; 486 K)
Solubility in water Insoluble
Hazards
GHS labelling:
Pictograms GHS07: Exclamation markGHS08: Health hazard
Signal word Danger
Hazard statements H315, H317, H319, H334, H335, H350
Precautionary statements P201, P261, P280, P305+P351+P338, P308+P313
Safety data sheet (SDS) External SDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒N verify (what is  ?) Infobox references
Chemical compound

Dichloronickel a coordination complex with the formula NiCl2(dppp); where dppp is the diphosphine 1,3-bis(diphenylphosphino)propane. It is used as a catalyst in organic synthesis. The compound is a bright orange-red crystalline powder.

Structure and properties

While the electronic and solid-state structure of the chloride congener is not known (due to low solubility in common analytical solvents), several studies have been carried out on the bromo and iodo derivatives. The complexes display a temperature-dependent interconversion between square-planar and tetrahedral geometries (diamagnetic and paramagnetic) in polar organic solvents (Keq between 1-3.68, depending on the solvent and temperature). In contrast, dichloro(1,2-bis(diphenylphosphino)ethane)nickel adopts a static square-planar (diamagnetic) structure in solution.

Preparation

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

Ni(H2O)6Cl2 + dppp → NiCl2(dppp) + 6 H2O

Reactions

NiCl2(dppp) in an effective catalyst for coupling reactions such as the Kumada coupling and Suzuki reactions (example below). It also catalyzes other reactions that convert enol ethers, dithioacetals, and vinyl sulfides to olefins.

References

  1. ^ "1,3-Bis(diphenylphosphino)propane Nickel(II) Chloride". American Elements. Retrieved September 6, 2018.
  2. Van Hecke, Gerald R.; Horrocks, Jr., William DeW. (1966). "Ditertiary Phosphine Complexes of Nickel. Spectral, Magnetic, and Proton Resonance Studies. A Planar-Tetrahedral Equilibrium". Inorganic Chemistry. 5 (11): 1968–1974. doi:10.1021/ic50045a029.
  3. ^ Kumada, Makota; Tamao, Kohei; Sumitani, Koji (1978). "Phosphine-Nickel Complex Catalyzed Cross-Coupling of Grignard Reagents with Aryl and Alkenyl Halides: 1,2-Dibutylbenzene". Org. Synth. 58: 127. doi:10.15227/orgsyn.058.0127.
  4. Zhao, Yu-Long; Li, You; Li, Shui-Ming; Zhou, Yi-Guo; Sun, Feng-Yi; Gao, Lian-Xun; Han, Fu-She (1 June 2011). "A Highly Practical and Reliable Nickel Catalyst for Suzuki-Miyaura Coupling of Aryl Halides". Advanced Synthesis & Catalysis. 353 (9): 1543–1550. doi:10.1002/adsc.201100101.
  5. Tien-Yau Luh; Tien-Min Yuan. "Cross-Coupling Reactions". Encyclopedia of Reagents for Organic Synthesis doi:10.1002/047084289X.rd100.pub2.
  6. Ljungdahl, Thomas; Bennur, Timmanna; Dallas, Andrea; Emtenaes, Hans; Maartensson, Jerker (2008). "Two Competing Mechanisms for the Copper-Free Sonogashira Cross-Coupling Reaction". Organometallics. 27 (11): 2490–2498. doi:10.1021/om800251s.
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