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|verifiedrevid = 425461791 |
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|ImageFile = Dichloro(1,3-bis(diphenylphosphino)propane)nickel.svg |
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|ImageSize = 120px |
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|Name = Dichloronickel |
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|SystematicName = Dichloronickel |
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|OtherNames = 1,3-bis(diphenyl{{SHY}}phosphino)propanenickel(II) chloride; |
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NiCl<sub>2</sub>(dppp) |
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{{DISPLAYTITLE:Dichloronickel}} <!-- Note that this line doesn't work yet due to software limitations on the use of square-brackets in title names |
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|CASNo_Ref = {{cascite|correct|??}} |
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| verifiedrevid = 400555409 |
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|CASNo = 15629-92-2 |
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| ImageFile = NiCl2(dppp).png |
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|PubChem = 6329934 |
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| OtherNames = 1,3-bis(diphenylphosphino)propanenickel(II) chloride |
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|EC_number = 605-052-3 |
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|ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| CASNo = 15629-92-2 |
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|ChemSpiderID = 2007051 |
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|SMILES = Cl1((c2ccccc2)(c3ccccc3)CCC1(c4ccccc4)c5ccccc5)Cl |
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|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;;; |
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| C=27|H=26|Cl=2|Ni=1|P=2 |
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| Appearance = Orange to yellow orange powder |
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| Solubility = immiscible in water |
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|C=27 | H=26 | Cl=2 | Ni=1 | P=2 |
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| MeltingPtC = 213 |
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|Appearance = Orange to red-orange powder |
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|Solubility = Insoluble |
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|MeltingPtC = 213 |
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| RPhrases = R49-36/37/38-42/43 |
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|Section3 = {{Chembox Hazards |
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| SPhrases = S53-26-36/37/39-45 |
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|GHSPictograms = {{GHS07}}{{GHS08}}<ref name=sds>{{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 = ]|accessdate = September 6, 2018}}</ref> |
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|GHSSignalWord = Danger<ref name=sds /> |
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|HPhrases = {{H-phrases|315|317|319|334|335|350}}<ref name=sds /> |
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|PPhrases = {{P-phrases|201|261|280|305+351+338|308+313}}<ref name=sds /> |
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'''Dichloronickel''' a ] with the formula NiCl<sub>2</sub>(dppp) (where dppp = Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>). It is used as a ] in organic synthesis. The compound is an orange crystalline powder. |
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'''Dichloronickel''' a ] with the formula NiCl<sub>2</sub>(dppp); where dppp is the ] ]. It is used as a ] in organic synthesis. The compound is a bright orange-red crystalline powder. |
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==Structure and properties== |
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==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.<ref>{{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}}</ref> 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, ] adopts a static square-planar (diamagnetic) structure in solution. |
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The compound exhibits ] with ] at the central nickel atom. The compound is soluble in non-polar organic solvents and is diamagnetic. |
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== Preparation == |
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== Preparation == |
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NiCl<sub>2</sub>(dppp) is prepared by combining equal molar portions of ] hexahydrate with ] in 2-propanol.<ref name = kumada>{{OrgSynth | author = Kumada, Makota; Tamao, Kohei; Sumitani, Koji | title = Phosphine-Nickel Complex Catalyzed Cross-Coupling of Grignard Reagents with Aryl and Alkenyl Halides: 1,2-dibutylbenzene | collvol = 6 | collvolpages = 407 | year = 1988 | prep = cv6p0407}}</ref> |
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NiCl<sub>2</sub>(dppp) is prepared by combining equal molar portions of ] hexahydrate with ] in 2-propanol.<ref name = kumada>{{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.}}</ref> |
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:Ni(H<sub>2</sub>O)<sub>6</sub>Cl<sub>2</sub> + dppp → NiCl<sub>2</sub>(dppp) + 6 H<sub>2</sub>O |
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:Ni(H<sub>2</sub>O)<sub>6</sub>Cl<sub>2</sub> + dppp → NiCl<sub>2</sub>(dppp) + 6 H<sub>2</sub>O |
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==Reactions== |
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==Reactions== |
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NiCl<sub>2</sub>(dppp) in an effective catalyst for ]s such as the ]<ref name = kumada/> and ]s (example below).<ref>{{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}}</ref> It also catalyzes other reactions that convert ]s, ]s, and vinyl sulfides to ].<ref>Tien-Yau Luh; Tien-Min Yuan. "Cross-Coupling Reactions". Encyclopedia of Reagents for Organic Synthesis {{doi|10.1002/047084289X.rd100.pub2}}.</ref><ref>{{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 = ] | volume = 27 | issue = 11 | pages = 2490–2498 | year = 2008 | doi = 10.1021/om800251s}}</ref> |
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It is used in Grignard reagent reactions involving cross-coupling of aryl halides, converting enol ethers, dithioacetals, and vinyl sulfides to olefins. NiCl<sub>2</sub>(dppp) is used because the douple phosphate ligand minimizes the reduction reactions with labile β-hydrogens.<ref>Sigma-Aldrich. CAS 15629-92-2.</ref> |
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Cross-coupling reactions of R-X compounds with organometallic nucleophiles are catalyzed by transition metal complexes such as NiCl<sub>2</sub>(dppp). The R group consists of aryl, vinyl, or allyl groups and the X group is a good leaving group. Cross-coupling reactions are effective at producing carbon-carbon bonds. Catalysts that have bidentate phosphine ligands serve as the best catalysts.<ref>Tien-Yau Luh; Tien-Min Yuan. ”Cross-Coupling Reactions”. Encyclopedia of Reagents for Organic Synthesis. DOI: 10.1002/047084289X.rd100.pub2.</ref> |
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NiCl<sub>2</sub>(dppp) serves as the catalyst by bonding the two cross-coupling components to the nickel. The cross-coupling proceeds by oxidative addition of the aryl, vinyl, or allyl halide to NiCl<sub>2</sub>(dppp) forming an oxidative addition adduct, R<sub>1</sub>-NiCl(dppp). The organometallic nucleophile, R<sub>2</sub>-MgBr, reacts with R<sub>1</sub>-NiCl(dppp) and is followed by the cross-coupling reaction producing the R<sub>1</sub>-R<sub>2</sub> product.<ref>{{cite journal | author = Ljungdahl, Thomas; Bennur, Timmanna; Dallas, Andrea; Emtenaes, Hans; Maartensson, Jerker | title = Two Competing Mechanisms for the Copper-Free Sonogashira Cross-Coupling Reaction | journal = ] | volume = 27 | issue = 11 | pages = 2490–2498 | year = 2008 | doi = 10.1021/om800251s}}</ref> |
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The compound is a catalyst for ] reactions involving alkyl, alkenyl, aryl, and heteroaryl Grignard reagents with aryl, heteroaryl, and alkenyl halides.<ref name = kumada/> |
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==References== |
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==References== |
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{{Reflist|1}} |
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