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

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Dichloro[1,3-bis(diphenyl­phosphino)propane]nickel
Names
Systematic IUPAC name
Dichloro[1,3-propanediylbis(diphenylphosphanuide-κP)]nickel
Other names
1,3-bis(diphenyl­phosphino)propanenickel(II) chloride; NiCl2(dppp)
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.132.628 Edit this at Wikidata
EC Number
  • 605-052-3
  • 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;;;
  • Cl[Ni]1([P](c2ccccc2)(c3ccccc3)CCC[P]1(c4ccccc4)c5ccccc5)Cl
Properties
C27H26Cl2NiP2
Molar mass 542.05 g·mol−1
Appearance Orange to red-orange powder
Melting point 213 °C (415 °F; 486 K)
Insoluble
Hazards
GHS labelling:
GHS07: Exclamation markGHS08: Health hazard[1]
Danger[1]
H315, H317, H319, H334, H335, H350[1]
P201, P261, P280, P305+P351+P338, P308+P313[1]
Safety data sheet (SDS) External SDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Dichloro[1,3-bis(diphenylphosphino)propane]nickel 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

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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.[2] 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

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

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

Reactions

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NiCl2(dppp) in an effective catalyst for coupling reactions such as the Kumada coupling[3] and Suzuki reactions (example below).[4] It also catalyzes other reactions that convert enol ethers, dithioacetals, and vinyl sulfides to olefins.[5][6]

References

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  1. ^ a b c d "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. ^ a b 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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