:Dichloro(1,3-bis(diphenylphosphino)propane)nickel
{{chembox
|Verifiedfields = changed
|Watchedfields = changed
|verifiedrevid = 425461791
|ImageFile = Dichloro(1,3-bis(diphenylphosphino)propane)nickel.svg
|ImageSize = 120px
|Name = Dichloro[1,3-bis(diphenyl{{SHY}}phosphino)propane]nickel
|SystematicName = Dichloro[1,3-propanediylbis(diphenylphosphanuide-κP)]nickel
|OtherNames = 1,3-bis(diphenyl{{SHY}}phosphino)propanenickel(II) chloride;
NiCl2(dppp)
|Section1 = {{Chembox Identifiers
|CASNo_Ref = {{cascite|correct|??}}
|CASNo = 15629-92-2
|PubChem = 6329934
|EC_number = 605-052-3
|ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
|ChemSpiderID = 2007051
|SMILES = Cl[Ni]1([P](c2ccccc2)(c3ccccc3)CCC[P]1(c4ccccc4)c5ccccc5)Cl
|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;;;
}}
|Section2 = {{Chembox Properties
|C=27 | H=26 | Cl=2 | Ni=1 | P=2
|Appearance = Orange to red-orange powder
|Solubility = Insoluble
|MeltingPtC = 213
}}
|Section3 = {{Chembox Hazards
|ExternalSDS = [https://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=US&language=en&productNumber=335363&brand=ALDRICH&PageToGoToURL=https%3A%2F%2Fwww.sigmaaldrich.com%2Fcatalog%2Fproduct%2Faldrich%2F335363%3Flang%3Den External SDS]
|GHSPictograms = {{GHS07}}{{GHS08}}{{cite web|title = 1,3-Bis(diphenylphosphino)propane Nickel(II) Chloride|url = https://www.americanelements.com/1-3-bis-diphenylphosphino-propane-nickel-ii-chloride-15629-92-2|publisher = American Elements|accessdate = September 6, 2018}}
|HPhrases = {{H-phrases|315|317|319|334|335|350}}
|PPhrases = {{P-phrases|201|261|280|305+351+338|308+313}}
}}
}}
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
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.{{cite journal |last1=Van Hecke |first1=Gerald R. |last2=Horrocks, Jr. |first2=William DeW. |title=Ditertiary Phosphine Complexes of Nickel. Spectral, Magnetic, and Proton Resonance Studies. A Planar-Tetrahedral Equilibrium |journal=Inorganic Chemistry |date=1966 |volume=5 |issue=11 |pages=1968–1974 |doi=10.1021/ic50045a029}} 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.{{cite journal| last1= Kumada|first1=Makota|last2=Tamao|first2=Kohei|last3=Sumitani|first3=Koji | title = Phosphine-Nickel Complex Catalyzed Cross-Coupling of Grignard Reagents with Aryl and Alkenyl Halides: 1,2-Dibutylbenzene | volume = 58 | page = 127 | year = 1978 |doi = 10.15227/orgsyn.058.0127|journal=Org. Synth.}}
: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).{{cite journal|last=Zhao|first=Yu-Long|author2=Li, You |author3=Li, Shui-Ming |author4=Zhou, Yi-Guo |author5=Sun, Feng-Yi |author6=Gao, Lian-Xun |author7= Han, Fu-She |title=A Highly Practical and Reliable Nickel Catalyst for Suzuki-Miyaura Coupling of Aryl Halides|journal=Advanced Synthesis & Catalysis|date=1 June 2011|volume=353|issue=9|pages=1543–1550|doi=10.1002/adsc.201100101}} It also catalyzes other reactions that convert enol ethers, dithioacetals, and vinyl sulfides to olefins.Tien-Yau Luh; Tien-Min Yuan. "Cross-Coupling Reactions". Encyclopedia of Reagents for Organic Synthesis {{doi|10.1002/047084289X.rd100.pub2}}.{{cite journal |author1=Ljungdahl, Thomas |author2=Bennur, Timmanna |author3=Dallas, Andrea |author4=Emtenaes, Hans |author5=Maartensson, Jerker | title = Two Competing Mechanisms for the Copper-Free Sonogashira Cross-Coupling Reaction | journal = Organometallics | volume = 27 | issue = 11 | pages = 2490–2498 | year = 2008 | doi = 10.1021/om800251s}}
