| Revision as of 03:45, 14 June 2011 editRifleman 82 (talk | contribs)Extended confirmed users32,435 edits both cis and trans known← Previous edit |
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{{Chembox |
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| verifiedrevid = 396300653 |
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| verifiedrevid = 434174203 |
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| ImageFile = Bis(triphenylphosphine)palladium(II)_dichloride.png |
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| ImageFile1 = Trans-dichlorobis(triphenylphosphine)palladium(II)-2D.png |
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| ImageSize1 = 175 |
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| ImageFile1 = Dichlorobis(triphenylphosphine)palladium(II).jpg |
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| ImageFile2 = Trans-dichlorobis(triphenylphosphine)palladium(II)-from-xtal-3D-balls.png |
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| ImageFile3 = Dichlorobis(triphenylphosphine)palladium(II).jpg |
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| IUPACName = |
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| IUPACName = |
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| OtherNames = |
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| OtherNames = |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| InChI = 1/2C18H15P.2ClH.Pd/c2*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h2*1-15H;2*1H;/q;;;;+2/p-2 |
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| InChI = 1/2C18H15P.2ClH.Pd/c2*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h2*1-15H;2*1H;/q;;;;+2/p-2 |
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| SMILES = ...c3c(P(c1ccccc1)c2ccccc2)cccc3.c1ccccc1P(c2ccccc2)c3ccccc3 |
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| SMILES = ...c3c(P(c1ccccc1)c2ccccc2)cccc3.c1ccccc1P(c2ccccc2)c3ccccc3 |
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| SMILES_Comment = ionic form |
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| SMILES1 = Cl(Cl)((c0ccccc0)(c0ccccc0)(c0ccccc0))(c0ccccc0)(c0ccccc0)(c0ccccc0) |
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| SMILES1_Comment = coordination form |
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| InChIKey = YNHIGQDRGKUECZ-NUQVWONBAO |
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| InChIKey = YNHIGQDRGKUECZ-NUQVWONBAO |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo =13965-03-2 |
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| CASNo =13965-03-2 |
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| PubChem = 6102075 |
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| PubChem = 6102075 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 75895 |
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| ChemSpiderID = 75895 |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| C = 36 | H= 30 | Cl = 2 | P = 2 | Pd =1 |
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| C=36 | H=30 | Cl=2 | P=2 | Pd=1 |
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| Formula = PdCl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> |
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| Appearance = |
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| Appearance = yellow powder |
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| Density = |
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| MeltingPt = |
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| Density = |
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| MeltingPt = 260 °C (decomposed around 300 °C) |
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| BoilingPt = |
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| Solubility = |
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| BoilingPt = |
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| Solubility = insoluble |
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| SolubleOther = soluble in chloroform, hexane, toluene, benzene, acetone<ref name="chemspider">{{cite web |url=https://www.chemspider.com/Chemical-Structure.75895.html |title=PdCl2(PPh3)2 |website=] |access-date=2 January 2024}}</ref> |
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| Section3 = {{Chembox Hazards |
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|Section3={{Chembox Hazards |
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| MainHazards = |
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| FlashPt = |
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| NFPA-H = 2 |
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| Autoignition = |
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| NFPA-F = 1 |
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| NFPA-R = 0 |
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| FlashPt = 181.7 °C |
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| AutoignitionPt = |
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|Section4={{Chembox Related |
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| OtherCompounds = ] |
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'''Bis(triphenylphosphine)palladium(II) dichloride''' is a ] of ] containing two ] and two ] ligands. This yellow complex is often used for ], e.g. the ]. The complex is ]. Both ''cis'' and ''trans'' isomers are known. |
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'''Bis(triphenylphosphine)palladium chloride''' is a ] of ] containing two ] and two ] ligands. It is a yellow solid that is soluble in some organic solvents. It is used for ], e.g. the ]. The complex is ]. Many analogous complexes are known with different phosphine ligands. |
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Commercially available, this compound may be prepared by reacting ] with triphenylphosphine:<ref>{{OrgSynth | title = Palladium-catalyzed reaction of 1-alkenylboronates with vinylic halides: (1Z,3E)-1-Phenyl-1,3-octadiene | collvol = 8 | collvolpages = 532 | author = Norio Miyaura and Akira Suzuki | year = 1993 | prep = cv8p0532}}</ref> |
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==Preparation and reactions== |
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:PdCl<sub>2</sub> + 2 PPh<sub>3</sub> → PdCl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> |
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This compound may be prepared by treating ] with ]:<ref>{{cite journal | title = Palladium-Catalyzed Reaction of 1-Alkenylboronates with Vinylic Halides: (1Z,3E)-1-Phenyl-1,3-octadiene | journal = Organic Syntheses | volume = 68 | page = 130 |author1-link=Norio Miyaura | author1 = Norio Miyaura|author2-link=Akira Suzuki (chemist)|author2=Akira Suzuki | year = 1990 | doi=10.15227/orgsyn.068.0130}}</ref><ref>{{cite journal | title = Homogeneous Catalysis in the Reactions of olefinic Substances. V.Hydrogenation of Soybean Oil Methyl Ester with Triphenylphosphine and Triphenylarsine Palladium Catalysts| volume = 44 | page = 147 |author=Hiroshi Itatani |author2=J.C.Bailar | year = 1967 |journal=Journal of the American Oil Chemists' Society|doi=10.1007/BF02558176| s2cid = 93580917 }}</ref> |
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The complex is an intermediate in the preparation of ] (Pd(PPh<sub>3</sub>)<sub>4</sub>):<ref>{{cite journal | journal = ] | volume = 13 | pages = 121 | title = 23. Tetrakis(triphenylphosphine)palladium(0) | author = D. R. Coulson | doi = 10.1002/9780470132449.ch23 | year = 1972 | last2 = Satek | first2 = L. C. | last3 = Grim | first3 = S. O.}}</ref> |
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:PdCl<sub>2</sub> + 2 PPh<sub>3</sub> → PdCl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> |
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Upon reduction with ] in the presence of excess triphenylphosphine, the complex is a precursor to ], Pd(PPh<sub>3</sub>)<sub>4</sub>:<ref>{{cite book | journal = ] | volume = 13 | pages = 121–124 | chapter = Tetrakis(triphenylphosphine)palladium(0) | author = D. R. Coulson | title = Inorganic Syntheses | doi = 10.1002/9780470132449.ch23 | year = 1972| isbn = 978-0-470-13244-9 }}</ref> |
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:2 PdCl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> + 4 PPh<sub>3</sub> + 5 N<sub>2</sub>H<sub>4</sub> → 2 Pd(PPh<sub>3</sub>)<sub>4</sub> + N<sub>2</sub> + 4 N<sub>2</sub>H<sub>5</sub><sup>+</sup>Cl<sup>−</sup> |
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==Structure== |
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:PdCl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> + 2 PPh<sub>3</sub> + 2.5 ] → Pd(PPh<sub>3</sub>)<sub>4</sub> + 0.5 N<sub>2</sub> + 2 N<sub>2</sub>H<sub>5</sub><sup>+</sup>Cl<sup>-</sup> |
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Several ]s containing PdCl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> have been reported. In all of the structures, PdCl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> adopts a ] and the ].<ref>{{cite journal|journal=Acta Crystallogr.|year=1982|volume=B38|issue=10|pages=2679–2681 |
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|doi=10.1107/S0567740882009583|title=''trans''-Dichlorobis(triphenylphosphine)palladium(II)|author1=G. Ferguson |author2=R. McCrindle |author3=A. J. McAlees |author4=M. Parvez |doi-access=}}</ref><ref>{{ cite journal | journal = ] | volume = 62 | year = 2006 | pages = m1324–m1325 | title = ''trans''-Dichlorobis(triphenylphosphine)palladium(II) dichloromethane solvate | author = G. Steyl | issue = 6 | doi = 10.1107/S1600536806017521 }}</ref><ref>{{ cite journal | journal = ] | volume = 64 | year = 2008 | page = m621 | title = ''trans''-Dichloridobis(triphenylphosphine)palladium(II) |author=J. Pons |author2=J. García-Antón |author3=X. Solans |author4=M. Font-Bardia |author5=J. Ros | issue = Pt 5 | doi = 10.1107/S1600536808008337 | pmid = 21202176 | pmc = 2961313 | doi-access = free }}</ref><ref>{{ cite journal | journal = ] | volume = 841 | year = 2017 | pages = 31–38 | title = Crystal structure of a novel polymorph of ''trans''-dichlorobis (triphenylphosphine) palladium (II) and its application as a novel, efficient and retrievable catalyst for the amination of aryl halides and stille cross-coupling reactions |author=A. Naghipour |author2=] |author3=H. Babaee |author4=M. Hashemi |author5=B. Notash | doi = 10.1016/j.jorganchem.2016.10.002 }}</ref> |
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==Applications== |
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The complex is used as a pre-catalyst for a variety of coupling reactions.<ref>{{cite journal | title =One-Pot Procedure for the Synthesis of Unsymmetrical Diarylalkynes | volume = 75 | issue = 10 | pages = 3518–352 |author=René Severin |author2=Jessica Reimer |author3=Sven Doye | year = 2010 | journal = J. Org. Chem. | doi = 10.1021/jo100460v| pmid = 20420397 }}</ref> |
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The ] was once limited by high levels of catalyst and the limited availability of boronic acids. Replacements for halides were also found, increasing the number of coupling partners for the halide or pseudohalide as well. Using bis(triphenylphosphine)palladium chloride as the catalyst, triflates and ] have been coupled on an 80 kilogram scale in good yield.<ref>{{cite journal |author=Jacks, T. E. |author2=Belmont, Daniel T. |author3=Briggs, Christopher A. |author4=Horne, Nicole M. |author5=Kanter, Gerald D. |author6=Karrick, Greg L. |author7=Krikke, James J. |author8=McCabe, Richard J. |author9=Mustakis, Jason G. |author10=Nanninga, Thomas N.|year=2004|title=Development of a Scalable Process for CI-1034, an Endothelin Antagonist|journal=Organic Process Research & Development|volume=8|issue=2|pages=201–212|doi=10.1021/op034104g}}</ref> The same catalyst is effective for the ].<ref>{{cite journal |author=Chinchilla, R. |author2=Nájera, C.|year=2007|title=The Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry|journal=Chem. Rev.|volume=107|issue=3|pages=874–922|doi=10.1021/cr050992x|pmid=17305399}}</ref> |
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==See also== |
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* ] |
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* ] |
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==References== |
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==References== |
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{{Palladium compounds}} |
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{{Palladium compounds}} |
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