Wikipedia:WikiProject Chemicals/Chembox validation/VerifiedDataSandbox and Palladium(II) acetate: Difference between pages

|Watchedfields = changed

|verifiedrevid = 476992865

|Name = Palladium(II) acetate

<!--sample of palladium acetate trimer (recrystallized from benzene), Pd(OAc)2-->

|ImageName = Palladium(II) acetate

|ImageFile1 = Palladium(II)-acetate-2D.png

|ImageFile2 = Pd(OAc)2.jpg

|ImageFileL3 = Pd(OAc)2-trimer-from-xtal-Mercury-3D-balls-A.png

|ImageFileR3 = Polymeric-Pd(OAc)2-from-xtal-2004-Mercury-3D-balls-A.png

|ImageSizeR3 = 180

|IUPACName = Palladium(II) acetate

|OtherNames = Palladium diacetate<br />hexakis(acetato)tripalladium<br />bis(acetato)palladium

|Section1={{Chembox Identifiers

|CASNo_Ref = {{cascite|correct|CAS}}

|CASNo = 3375-31-3

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|ChemSpiderID = 146827

|EC_number = 222-164-4

|PubChem = 167845

|UNII_Ref = {{fdacite|correct|FDA}}

|UNII = 0LTG3460Y5

|RTECS = AJ1900000

|InChI = 1/2C2H4O2.Pd/c2*1-2(3)4;/h2*1H3,(H,3,4);/q;;+2/p-2

|InChIKey = YJVFFLUZDVXJQI-NUQVWONBAH

|StdInChI_Ref = {{stdinchicite|correct|chemspider}}

|StdInChI = 1S/2C2H4O2.Pd/c2*1-2(3)4;/h2*1H3,(H,3,4);/q;;+2/p-2

|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

|StdInChIKey = YJVFFLUZDVXJQI-UHFFFAOYSA-L

|SMILES = [Pd+2].[O-]C(=O)C.[O-]C(=O)C

|SMILES_Comment = ionic form

|SMILES1 = O0[C-](C)O[Pd+2]3(O[C-](C)O1)O[C-](C)O[Pd+2]1(O[C-](C)O2)O[C-](C)O[Pd-2]02O[C-](C)O3

|SMILES1_Comment = coordination form (cyclic trimer)

|Section2={{Chembox Properties

|Formula = Pd(CH₃COO)₂

|MolarMass = 224.51 g/mol

|Appearance = Brown yellow solid

|Density = 2.19 g/cm³

|Solubility = low

|MeltingPtC = 205

|MeltingPt_notes = decomposes

}}

|Section3={{Chembox Structure

|Coordination = square planar

|CrystalStruct = [[monoclinic]]

|Dipole = 0 [[Debye|D]]

}}

|Section7={{Chembox Hazards

|ExternalSDS = [http://msds.gfschemicals.com/atn/PALLADIUM%20ACETATE%2c%2098%25_Default_SDS%20US.pdf]

|MainHazards = considered nonhazardous

|GHS_ref=<ref>{{cite web |title=520764 [Pd(OAc)2]3 |url=https://www.sigmaaldrich.com/AU/en/product/aldrich/520764 |publisher=Sigma-Aldrich |access-date=23 December 2021}}</ref>

|GHSPictograms = {{GHS05}}{{GHS07}}{{GHS09}}

|GHSSignalWord = Danger

|HPhrases = {{H-phrases|H317|H318|H410}}

|PPhrases = {{P-phrases|P261|P272|P273|P280|P302+P352|P305+P351+P338}}

}}

|Section8={{Chembox Related

|OtherAnions = [[Palladium(II) chloride]]

|OtherCations = [[Platinum(II) acetate]]

}}

}}

'''Palladium(II) acetate''' is a [[chemical compound]] of [[palladium]] described by the formula [Pd(O₂CCH₃)₂]_n, abbreviated [Pd(OAc)₂]_n. It is more reactive than [[Platinum(II) acetate|the analogous platinum compound]]. Depending on the value of n, the compound is soluble in many organic solvents and is commonly used as a catalyst for organic reactions.<ref>{{cite book |doi=10.1002/047084289X.rp001.pub3 |chapter=Palladium(II) Acetate |title=Encyclopedia of Reagents for Organic Synthesis |date=2001 |last1=Grennberg |first1=Helena |last2=Foot |first2=Jonathan S. |last3=Banwell |first3=Martin G. |last4=Roman |first4=Daniela Sustac |pages=1–35 |isbn=978-0-470-84289-8 }}</ref>

==Structure==

With a 1:2 stoichiometric ratio of palladium atoms and acetate [[ligand]]s, the compound exists as molecular and polymeric forms with the trimeric form being the dominant form in the solid state and in solution. Pd achieves approximate [[square planar coordination]] in both forms.

As prepared by [[Geoffrey Wilkinson]] and coworkers in 1965 and later characterized by Skapski and Smart in 1970 by single crystal X-ray diffraction, palladium(II) acetate is a red-brown solid that [[crystallizes]] as monoclinic plates. It has a trimeric structure, consisting of an equilateral triangle of Pd atoms each pair of which is bridged with two acetate groups in a butterfly conformation.<ref name = stephenson>{{cite journal |doi = 10.1039/jr9650003632 |title = 667. Carboxylates of palladium, platinum, and rhodium, and their adducts |year = 1965 |author1=T. A. Stephenson |author2=S. M. Morehouse |author3=A. R. Powell |author4=J. P. Heffer |author5-link = Geoffrey Wilkinson |author5=G. Wilkinson |journal = Journal of the Chemical Society (Resumed) | page = 3632}}</ref><ref name=Skapski>{{cite journal |author1=Skapski, A C. |author2=M. L. Smart |title = The Crystal Structure of Trimeric Palladium(II) Acetate |journal = J. Chem. Soc. D |year = 1970 |pages = 658b–659 |doi = 10.1039/C2970000658b |issue = 11}}</ref>

Palladium(II) acetate can also be prepared as a pale pink form. According to X-ray powder diffraction, this form is polymeric.<ref name=Kirik>{{cite journal |author1=Kirik, S.D. |author2=Mulagaleev, S.F. |author3=Blokhin, A.I. |journal = [[Acta Crystallogr. C]]|year = 2004 |pages = m449–m450 |doi = 10.1107/S0108270104016129|title=[Pd(CH₃COO)₂]_n from X-ray Powder Diffraction Data |volume=60 |issue=9|pmid=15345831 }}</ref>

==Preparation==

Palladium acetate, in trimeric form, can be prepared by treating palladium sponge with a mixture of [[acetic acid]] and [[nitric acid]]. An excess of palladium [[sponge metal]] or nitrogen gas flow are required to prevent contamination by the mixed nitrito-acetate (Pd₃(OAc)₅NO₂).<ref name=bakhmutov>{{cite journal |author1=Bakhmutov, V. I. |author2=Berry, J. F. |author3=Cotton, F. A. |author4=Ibragimov, S. |author5=Murillo, C. A. |title = Non-Trivial Behavior of Palladium(II) Acetate|journal =[[Dalton Transactions]]|year = 2005 |pages = 1989–1992 |doi = 10.1039/b502122g |pmid = 15909048 |issue = 11}}</ref><ref>{{cite web|title=High Purity Homogeneous Catalyst |publisher=[[Engelhard]]|date=September 2005 |access-date=24 February 2006 |url=http://www.engelhard.com/documents/High%20Purity%20Homo%20Cat%20_Pd-acetate_%20A4%20Revised%20Final.pdf |archive-url=https://web.archive.org/web/20060317123128/http://www.engelhard.com/documents/High%20Purity%20Homo%20Cat%20_Pd-acetate_%20A4%20Revised%20Final.pdf |archive-date=17 March 2006 }}</ref>

:{{chem2 | Pd + 4 HNO3 -> Pd(NO3)2 + 2 NO2 + 2 H2O }}

:{{chem2 | Pd(NO3)2 + 2 CH3COOH -> Pd(O2CCH3)2 + 2 HNO3 }}

Relative to the trimeric acetate, the mixed nitrate-acetate variant has different solubility and catalytic activity. Preventing, or controlling for the amount of, this impurity can be an important aspect for reliable use of palladium(II) acetate.<ref name="C&EN May 2016">{{cite journal |volume= 94 |issue= 18 |pages= 20–21 |date= May 2, 2016 |title= Chemists introduce a user's guide for palladium acetate |first= Stephen K. |last= Ritter |journal= [[Chemical & Engineering News]] |doi=10.1021/cen-09418-scitech1}}</ref>

Palladium(II) propionate is prepared analogously; other [[Carboxylate|carboxylates]] are prepared by treating palladium(II) acetate with the appropriate [[carboxylic acid]].<ref name = stephenson/> Likewise, palladium(II) acetate can be prepared by treating other palladium(II) carboxylates with acetic acid. This ligand exchange starting with a purified other carboxylate is an alternative way to synthesize palladium(II) acetate free from the nitro contaminant.<ref name="C&EN May 2016"/>

Palladium(II) acetate is prone to reduction to Pd(0) in the presence of reagents which can undergo [[Beta-Hydride elimination|beta-hydride elimination]] such as primary and secondary alcohols as well as [[Amine|amines]]. When warmed with alcohols, or on prolonged boiling with other solvents, palladium(II) acetate [[Decompose|decomposes]] to palladium.<ref name = stephenson/>

==Catalysis==

{{see also|Palladium-catalyzed coupling reactions}}

Palladium acetate is a catalyst for many organic reactions, especially [[Alkene|alkenes]], [[diene]]s, and alkyl, aryl, and [[Vinyl halide|vinyl halides]] to form reactive adducts.<ref name=suggs>Suggs, J W. "Palladium: Organometallic Chemistry." Encyclopedia of Inorganic Chemistry. Ed. R B. King. 8 vols. Chichester: Wiley, 1994.</ref>

Reactions catalyzed by palladium(II) acetate:

*[[Vinylation]]: An example is the [[Heck reaction]] and related processes.<ref>{{cite journal|title=Ligand-Accelerated ortho-C-H Olefination of Phenylacetic Acids|author=Keary M. Engle |author2=Navid Dastbaravardeh |author3=Peter S. Thuy-Boun |author4=Dong-Hui Wang |author5=Aaron C. Sather |author6=Jin-Quan Yu |journal=Org. Synth.|year=2015|volume=92|pages=58–75|doi=10.15227/orgsyn.092.0058|pmc=4936495|pmid=27397943}}</ref>

*Rearrangement of acyclic dienes: An example is the [[Cope rearrangement]]

*[[Carbonylation]] reactions: for example, the formation of esters from aryl iodides, [[carbon monoxide]], an alcohol or phenol.<ref name="Nikitin1991">{{cite journal|last=Nikitin|first=Kirill V.|author2=Andryukhova, N.P. |author3=Bumagin, N.A. |author4= Beletskaya, I.P. |year=1991|title=Synthesis of Aryl Esters by Pd-catalysed Carbonylation of Aryl Iodides|journal=Mendeleev Communications|volume=1|issue=4|pages=129–131|doi=10.1070/MC1991v001n04ABEH000080}}</ref>

*[[Reductive amination]] of aldehydes or [[Ketone|ketones]] by potassium formate.<ref name=basu>{{cite journal | author = Basu, B., Satadru J., Mosharef H. B., and Pralay D. | title = A Simple Protocol for the Direct Reductive Amination of Aldehydes and Ketones Using Potassium Formate and Catalytic Palladium Acetate | journal = [[ChemInform]] | volume = 34 | issue = 30 | year = 2003 | pages = 555–557 | doi = 10.1002/chin.200330069}}</ref>

*[[Wacker process]]: the oxidation of [[ethylene]] by water to [[acetaldehyde]] (precursor to poly(vinyl acetate).

*[[Buchwald-Hartwig amination]] of [[aryl halide]]s/pseudohalides with alkyl an aryl amines.<ref>{{cite journal|title=Synthesis of α-Carboline

|author=Linli He |author2=Shawn P. Allwein |author3=Benjamin J. Dugan |author4=Kyle W. Knouse |author5=Gregory R. Ott |author6=Craig A. Zificsak |journal=Org. Synth.|year=2016|volume=93|page=272|doi=10.15227/orgsyn.093.0272|doi-access=free}}</ref><ref name=Buchwald>{{cite web | publisher = Organic Chemistry Portal | url = https://www.organic-chemistry.org/namedreactions/buchwald-hartwig-reaction.shtm | title = Buchwald-Hartwig Cross Coupling Reaction}}</ref>

*conversion of aryl bromides into the [[Trimethylsilane|trimethylsilanes]], a functional group in many organic compounds including the fungicide "Latitude".

:{{chem2 | RC6H4Br + Si2(CH3)6 -> RC6H4Si(CH3)3 + Si(CH3)3Br }}

Pd(O₂CCH₃)₂ is compatible with the electronic properties of aryl bromides, and unlike other methods of synthesis, this method does not require high pressure equipment.<ref name=gooben>Gooben, L J. "Research Area "New Pd-Catalyzed Cross-Coupling Reactions"" 28 Feb. 2006<http://www.mpi-muelheim.mpg.de/kofo/bericht2002/pdf/2.1.8_gossen.pdf> {{webarchive |url=https://web.archive.org/web/20070712180504/http://www.mpi-muelheim.mpg.de/kofo/bericht2002/pdf/2.1.8_gossen.pdf |date=July 12, 2007}}</ref>

==Precursor to other Pd compounds==

Palladium acetate is used to produce other palladium(II) compounds. For example, phenylpalladium acetate, used to isomerize allyl alcohols to [[aldehydes]], is prepared by the following reaction:<ref name=heck>{{OrgSynth|author=[[Richard F. Heck]]|title=Aldehydes from Allylic Alcohols and Phenylpalladium Acetate: 2-Methyl-3-Phenylpropionaldehyde|collvol=6|collvolpages=815|prep=cv6p0815}}</ref>

<!--what is the structure of "phenylpalladium acetate"? probably not a monoPd thing-->

:{{chem2 | Hg(C6H5)(OAc) + Pd(OAc)2 -> Pd(C6H5)(OAc) + Hg(OAc)2 }}

Palladium(II) acetate reacts with [[acetylacetone]] (the "acac" ligand) to produce [[Palladium(II) acetylacetonate|Pd(acac)₂]].

[[Herrmann's catalyst]] is made by reaction of palladium(II) acetate with [[tris(o-tolyl)phosphine|tris(''o''-tolyl)phosphine]].<ref>{{cite journal|author=Herrmann, W. A.|author2=Brossmer, C.|author3=Reisinger, C.-P.|author4=Riermeier, T. H.|author5=Öfele, K.|author6=Beller, M.|title=Palladacycles: Efficient New Catalysts for the Heck Vinylation of Aryl Halides|journal=Chemistry – A European Journal|year=1997|volume=3|pages= 1357–1364|doi=10.1002/chem.19970030823}}</ref>

:[[File:HerrmannCat.png|thumb|left|Structure of [[Herrmann's catalyst]].<ref>{{cite journal|author1=Herrmann, W. A. |author2=Brossmer, C. |author3=Reisinger, C.-P. |author4=Riermeier, T. H. |author5=Öfele, K. |author6=Beller, M. |title=Palladacycles: Efficient New Catalysts for the Heck Vinylation of Aryl Halides|journal=Chemistry – A European Journal|year=1997|volume=3|issue=8 |pages= 1357–1364|doi=10.1002/chem.19970030823}}</ref>]]{{clear-left}}

Light or heat reduce palladium acetate to give thin layers of palladium and can produce [[nanowire]]s and [[colloid]]s.<ref name=bakhmutov/>

==See also==

* [[Saegusa–Ito oxidation]]

==References==

{{reflist}}

{{Palladium compounds}}

{{clear}}

{{Acetates}}

[[Category:Palladium compounds]]

[[Category:Acetates]]