Palladium(II) acetate
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| Palladium(II) acetate | |
|---|---|
_acetate.jpg/200px-Palladium(II)_acetate.jpg) |
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| IUPAC name | Palladium(II) acetate |
| Other names | Palladium diacetate hexakis(acetato)tripalladium bis(acetato)palladium |
| Identifiers | |
| CAS number | [3375-31-3] |
| RTECS number | AJ1900000 |
| SMILES | C(CO)OPdO(CO)C |
| Properties | |
| Molecular formula | C4H6O4Pd |
| Molar mass | 224.50 g/mol |
| Appearance | Brown yellow solid |
| Density | 2.19 g/cm³ |
| Melting point |
205 °C (478 K), decomposes |
| Boiling point |
decomp. |
| Solubility in water | low |
| Structure | |
| Crystal structure | monoclinic |
| Coordination geometry |
Square Planar |
| Dipole moment | 0 D |
| Hazards | |
| MSDS | MSDS |
| Main hazards | considered nonhazardous |
| R-phrases | 41 |
| S-phrases | 24/25 |
| Related compounds | |
| Other anions | Palladium(II) chloride |
| Other cations | Platinum(II) acetate |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references |
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Palladium(II) acetate is a chemical compound of palladium described by the formula Pd(O2CCH3)2 or Pd(OAc)2. It is considered more reactive than the related platinum. It is soluble in many organic solvents.
Contents |
[edit] Structure
Palladium(II) acetate is trimeric, consisting of an equilateral triangle of Pd atoms each pair of which is bridged with two acetate groups in a butterfly conformation. Each metal atom achieves approximate square planar co-ordination.[1]
[edit] Preparation
It can be prepared in two steps from palladium sponge, hot glacial acetic acid, and nitric acid via the intermediacy of the dinitrate:[2]
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- Pd + 2 HNO3 → Pd(NO3)2 + H2
- Pd(NO3)2 + 2 CH3COOH → Pd(O2CCH3)2 + 2 HNO3
An excess of palladium sponge is used to insure that all HNO3 is consumed.
[edit] Uses
Palladium acetate is a catalyst for many organic reactions by combining with many common classes of organic compounds such as alkenes, dienes, and alkyl, aryl, and vinyl halides to form reactive adducts. Alkenes and π-allyl coordination to palladium(II) acetate involves sigma-type donation from the pi orbital of the alkene or π-allyl with concomitant pi-backbonding into an empty pi* orbital on the alkene or π-allyl. The greater the sigma donation to the metal is, the greater the pi-backbonding. The greater the pi-backbonding is, the greater the reduction in the bond order of the alkene or π-allyl.[3] Reduction of the alkenes or π-allyl by coordination to palladium(II) acetate reverses the reactivity of the organic ligand allowing them to undergo reactions with nucleophiles rather than electrophiles.[4]
Examples of palladium(II) acetate catalyzed reactions are:
- Vinylation: An example is the Heck reaction
- Rearrangement of Acyclic Dienes: An example is the Cope reaction
- Carbonylation reaction: carboxylation of aryl halides and benzyl chloride derivatives in ionic liquid media (l-butyl-3-methylimidazolium hexafluorophosphate, tetrafluoroborate, and Aliquat336 )
- Reductive amination of aldehydes or ketones using potassium formate.[5]
- Wacker process: the oxidation of ethylene in water to form acetaldehyde (precursor to poly(vinyl acetate), a common glue).
- Buchwald-Hartwig synthesis of aryl amines from aryl halides/pseudohalides and primary or secondary amines.[6]
Pd(O2CCH3)2 converts aryl bromides into aryltrimethylsilanes, an important functional group in many organic compounds including the fungicide "Latitude".
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- 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.[7]
[edit] Precursor to other Pd compounds
Palladium acetate is used to produce other palladium(II) compounds. For example, phenylpalladium acetate, used to isomerize allylic alcohols to aldehydes, is prepared by the following reaction:
Hg(C6H5)(CH3COO) + Pd(CH3COO)2 → Pd(C6H5)(O2CCH3) + Hg(O2CCH3)2[8]
Palladium(II) acetate reacts with acetylacetone to produce Pd(acac)2, a precursor to Pd(0).[citation needed]
Light or heat reduce palladium acetate to give thin layers of palladium and can produce nanowires and colloids.[2]
[edit] References
- ^ Skapski, A C.; M. L. Smart (1970). "The Crystal Structure of Trimeric Palladium(II) Acetate". J. Chem. Soc. D: 658b-659. doi:.
- ^ a b Bakhmutov, V. I.,; Berry, J. F.; Cotton, F. A.; Ibragimov, S.; Murillo, C. A. (2005). "Non-Trivial Behavior of Palladium (II) Acetate". Dalton Transactions: 1989–1992. doi:.
"High Purity Homogeneous Catalyst." Engelhard. Sept. 2005. Engelhard Corp. 24 Feb. 2006.<http://www.engelhard.com/documents/High%20Purity%20Homo%20Cat%20_Pd-acetate_%20A4%20Revised%20Final.pdf>. - ^ Toreki, R. "Allyl Ligands." The Organometallic HyperTextBook. 20 Nov. 2003. Chemglass. 01 Apr. 2006<http://www.ilpi.com/organomet/allyl.html>.
- ^ Suggs, J W. "Palladium: Organometallic Chemistry." Encyclopedia of Inorganic Chemistry. Ed. R B. King. 8 vols. Chichester: Wiley, 1994.
- ^ Basu, B., Satadru J., Mosharef H. B., and Pralay D. (2003). "A Simple Protocol for the Direct Reductive Amination of Aldehydes and Ketones Using Potassium Formate and Catalytic Palladium Acetate". ChemInform 34 (30): 555–557. doi:.
- ^ Buchwald-Hartwig Cross Coupling Reaction. Organic Chemistry Portal.
- ^ 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>.
- ^ Richard F. Heck. "Aldehydes from Allylic Alcohols and Phenylpalladium Acetate: 2-Methyl-3-Phenylpropionaldehyde". Org. Synth.; Coll. Vol. 6: 815.
