Allylpalladium chloride dimer

Allylpalladium(II) chloride dimer
Names
	IUPAC name Allylpalladium(II) chloride dimer
	Other names Allylpalladium chloride dimer; bis(allyl)di-μ-chloro-dipalladium(II); APC
Identifiers
CAS Number	12012-95-2 ;
3D model (JSmol)	Interactive image;
ChemSpider	21171401 ;
ECHA InfoCard	100.031.423
EC Number	234-579-8;
PubChem CID	61538;
CompTox Dashboard (EPA)	DTXSID10897423;
	InChI InChI=1S/2C3H5.2ClH.2Pd/c21-3-2;;;;/h23H,1-2H2;21H;;/q;;;;2+1/p-2 Key: TWKVUTXHANJYGH-UHFFFAOYSA-L ; InChI=1/2C3H5.2ClH.2Pd/c21-3-2;;;;/h23H,1-2H2;21H;;/q;;;;2+1/p-2/r2C3H5ClPd/c21-2-3-5-4/h22H,1,3H2 Key: TWKVUTXHANJYGH-NNVIZEFPAF;
	SMILES Cl[Pd]CC=C.C=CC[Pd]Cl;
Properties
Chemical formula	C6H10Cl2Pd2
Molar mass	365.85 g/mol
Appearance	Pale yellow, crystalline solid
Melting point	decomp at 155-156 °C
Solubility in water	Insoluble
Solubility in other solvents	Chloroform; benzene; acetone; methanol
Structure
Crystal structure	monoclinic
Space group	P21/n, No. 14
Formula units (Z)	2
Hazards
	GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H302, H312, H315, H319, H332, H335
Precautionary statements	P261, P264, P270, P271, P280, P301+P312, P302+P352, P304+P312, P304+P340, P305+P351+P338, P312, P321, P322, P330, P332+P313, P337+P313, P362, P363, P403+P233, P405, P501
Safety data sheet (SDS)	http://www.colonialmetals.com/pdf/5048.pdf
Related compounds
Related compounds	(η3-allyl)(η5 – cyclopentadienyl)palladium(II); di-μ-chlorobis(crotyl)dipalladium
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Allylpalladium(II) chloride dimer (APC) is a chemical compound with the formula [(η³-C₃H₅)PdCl]₂. This yellow air-stable compound is an important catalyst used in organic synthesis.^[2] It is one of the most widely used transition metal allyl complexes.

Structure

The compound has a dimeric structure that is centrosymmetric. Each allyl group lies in a plane at an angle of about 111.5° to the square formed by the palladium and carbon atoms, and the Pd–C distances are all equal. Its unit cell is monoclinic.^[1]

Synthesis

sample of allyl palladium chloride dimer

The compound is prepared by purging carbon monoxide through a methanolic aqueous solution of sodium tetrachloropalladate (prepared from palladium(II) chloride and sodium chloride), and allyl chloride.^[2]

2 Na₂PdCl₄ + 2 CH₂=CHCH₂Cl + 2 CO + 2 H₂O → [(η³-C₃H₅)PdCl]₂ + 4 NaCl + 2 CO₂ + 4 HCl

Another method is the reaction of propene with palladium(II) trifluoroacetate, followed by ion exchange with chloride:^[3]

2 (CF₃COO)₂Pd + 2 CH₂=CHCH₃ → [(η³-C₃H₅)Pd(CF₃COO)]₂

[(η³-C₃H₅)Pd(CF₃COO)]₂ + 2 Cl⁻ → [(η³-C₃H₅)PdCl]₂ + 2 CF₃COO⁻

Reactions

APC reacts with sources of cyclopentadienyl anion to give the corresponding 18e⁻ complex cyclopentadienyl allyl palladium:

[(η³-C₃H₅)PdCl]₂ + 2 NaC₅H₅ → 2 [(η⁵-C₅H₅)Pd(η³-C₃H₅)] + 2 NaCl

The dimer reacts with a variety of Lewis bases (:B) to form adducts (η³-C₃H₅)PdCl:B. Its reaction with pyridine and the corresponding enthalpy are:

1/2 [(η³-C₃H₅)PdCl]₂ + :NC₅H₅ → (η³-C₃H₅)PdCl:NC₅H₅ ΔH=−30.1 kJ.mol⁻¹

This enthalpy corresponds to the enthalpy change for a reaction forming one mole of the product, (η³-C₃H₅)PdCl:NC₅H₅, from the acid dimer. The dissociation energy for the Pd dimer, which is an energy contribution prior to reaction with the donor,

[(η³-C₃H₅)PdCl]₂ → 2 (η³-C₃H₅)PdCl

has been determined by the ECW model to be 28 kJ.mol⁻¹.

APC catalyzes many organic reactions, such as cross-coupling, nucleophilic addition to dienes, and decomposition of diazo compounds to reactive carbenes. It is also a useful precursor of other Pd catalysts.^[3]

References

^ ^a ^b Smith, A. E. (1965). "The structure of the allylpalladium chloride complex (C3H5PdCl)2 at –140°C". Acta Crystallographica. 18 (3): 331–340. Bibcode:1965AcCry..18..331S. doi:10.1107/S0365110X65000774. ISSN 0365-110X.
^ ^a ^b Tatsuno, Y.; Yoshida, T.; Otsuka, S. "(η³-allyl)palladium(II) Complexes" Inorganic Syntheses, 1990, volume 28, pages 342-345. ISBN 0-471-52619-3
^ ^a ^b Godleski, Stephen A.; Michelet, Véronique; Genêt, Jean-Pierre (2006), "Bis(allyl)di-μ-chlorodipalladium", Encyclopedia of Reagents for Organic Synthesis, Chichester, UK: John Wiley & Sons, Ltd, doi:10.1002/047084289x.rb098s.pub2, ISBN 978-0-471-93623-7, retrieved 2020-09-06

[structure-1] Smith, A. E. (1965). "The structure of the allylpalladium chloride complex (C3H5PdCl)2 at –140°C". Acta Crystallographica. 18 (3): 331–340. Bibcode:1965AcCry..18..331S. doi:10.1107/S0365110X65000774. ISSN 0365-110X.

[Tatsuno-2] Tatsuno, Y.; Yoshida, T.; Otsuka, S. "(η³-allyl)palladium(II) Complexes" Inorganic Syntheses, 1990, volume 28, pages 342-345. ISBN 0-471-52619-3

[e-EROS-3] Godleski, Stephen A.; Michelet, Véronique; Genêt, Jean-Pierre (2006), "Bis(allyl)di-μ-chlorodipalladium", Encyclopedia of Reagents for Organic Synthesis, Chichester, UK: John Wiley & Sons, Ltd, doi:10.1002/047084289x.rb098s.pub2, ISBN 978-0-471-93623-7, retrieved 2020-09-06

[1]

[2]

[3]

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Allylpalladium chloride dimer

Structure

Synthesis

Reactions

References

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