12107-56-1

Basic information

• Product Name: Dichloro(1,5-cyclooctadiene)palladium(II)
• Synonyms: dichloro[(1,2,5,6-eta)-1,5-cyclooctadiene]-palladiu;(1,5-CYCLOOCTADIENE)PALLADIUM(II)CHLORIDE;1,5-CYCLOOCTADIENEPALLADIUM(II) DICHLORIDE;DICHLORO(CYCLOOCTA-1,5-DIENE)PALLADATE (II);DICHLORO(CYCLOOCTA-1,5-DIENE)PALLADIUM(II);DICHLORO(ETA-CYCLOOCTA-1,5-DIENE)PALLADIUM (II);DICHLORO(1,5-CYCLOOCTYLDIENE)PALLADIUM(II);DICHLORO(1,5-CYCLOOCTADIENE)PALLADIUM(II)
• CAS NO: 12107-56-1
• Molecular Formula: C₈H₁₂Cl₂Pd
• Molecular Weight: 285.51
• EINECS: 235-161-8
• Product Categories: Catalysts for Organic Synthesis;Classes of Metal Compounds;Homogeneous Catalysts;Metal Complexes;Pd (Palladium) Compounds;Synthetic Organic Chemistry;Transition Metal Compounds;Catalysis and Inorganic Chemistry;Homogeneous Pd Catalysts;Palladium;organometallic complexes;chemical reaction,pharm,electronic,materials;Pd
• Mol File: 12107-56-1.mol
• Article Data: 19

Chemical Properties

• Melting Point: 210 °C (dec.)(lit.)
• Boiling Point: 153.5 °C at 760 mmHg
• Flash Point: 31.7 °C
• Appearance: yellow/crystal
• Vapor Pressure: 4.25mmHg at 25°C
• Storage Temp.: Inert atmosphere,Room Temperature
• Solubility: Soluble in dichloromethane
• Water Solubility: insoluble
• Sensitive: Hygroscopic
• CAS DataBase Reference: Dichloro(1,5-cyclooctadiene)palladium(II)(CAS DataBase Reference)
• NIST Chemistry Reference: Dichloro(1,5-cyclooctadiene)palladium(II)(12107-56-1)
• EPA Substance Registry System: Dichloro(1,5-cyclooctadiene)palladium(II)(12107-56-1)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-37/39
• WGK Germany: 3
• TSCA: Yes
• Hazardous Substances Data: 12107-56-1(Hazardous Substances Data)

Usage

Chemical Properties

yellow

Uses

Different sources of media describe the Uses of 12107-56-1 differently. You can refer to the following data:
1. Dichloro(1,5-cyclooctadiene)palladium(II) is used as catalyst for C-C bond and C-N formation, used in Heck coupling of alkynes with alkenes, Suzuki cross-coupling of aryl bromides , allylic substitution of oximes with allylic acetate and methoxycarbonylation of iodobenzene.
2. Dichloro(1,5-cyclooctadiene)palladium(II) is a commonly used catalyst to protect alcohols as acetals by treating with 2-benzyloxy-1-propene; to synthesize bicyclooctanes from diethyl malonate and in alkene carbonylation. It can also be used to catalyze the Heck coupling of nonactivated vinyl phosphates with electron deficient alkenes; the synthesis of benzo[b]thiophenes from thioenols and to prepare an active catalyst for Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions.

InChI:InChI=1/C8H12.2ClH.Pd/c1-2-4-6-8-7-5-3-1;;;/h1-2,7-8H,3-6H2;2*1H;/q;;;+2/p-2/b2-1-,8-7-;;;

Synthetic route

1,5-cis,cis-cyclooctadiene (1552-12-1, 111-78-4) + palladium dichloride → dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1)

Conditions	Yield
Stage #1: palladium dichloride With hydrogenchloride In water Inert atmosphere; Schlenk technique; Stage #2: 1,5-cis,cis-cyclooctadiene In ethanol; water Inert atmosphere; Schlenk technique;	98%
Stage #1: palladium dichloride With hydrogenchloride In ethanol Stage #2: 1,5-cis,cis-cyclooctadiene In ethanol

palladium dichloride + 1,5-dicyclooctadiene (5259-72-3, 10060-40-9, 111-78-4) → dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1)

Conditions	Yield
In hydrogenchloride; ethanol for 0.333333h; liquid HCl;	96%
In methanol suspn. of PdCl2 (28.2 mmol) in MeOH reacted with COD (84.6 mmol) for 48 h at room temp. with stirring; filtered off, washed (MeOH), vacuum-dried;	91%
In methanol at 20℃; for 48h;	84%
With hydrogenchloride In water

hydrogenchloride (7647-01-0) + palladium dichloride + 1,5-dicyclooctadiene (5259-72-3, 10060-40-9, 111-78-4) → dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1)

Conditions	Yield
Stage #1: hydrogenchloride; palladium dichloride at 20℃; Inert atmosphere; Stage #2: cyclo-octa-1,5-diene for 0.333333h; Inert atmosphere;	95%

sodium chloride (7647-14-5) + palladium dichloride + 1,5-dicyclooctadiene (5259-72-3, 10060-40-9, 111-78-4) → dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1)

Conditions	Yield
In methanol for 19h;	93%

chloroform-d1 (865-49-6) + [Pd(acetonyl)Cl] + 1,5-dicyclooctadiene (5259-72-3, 10060-40-9, 111-78-4) → dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + [Pd(acetonyl)Cl(1,5-cyclooctadiene)] (1042309-89-6)

Conditions	Yield
In acetone under N2; cyclooctadiene added to suspn. of Pd complex in acetone; detd. by (1)H NMR spectra in CDCl3;

[Pd(acetonyl)Cl(1,5-cyclooctadiene)] (1042309-89-6) → dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1)

Conditions	Yield
In not given slowly decompd. in chlorinated solvents;

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 1-[N,N’,N’’-trimethyl-(4-butyl)ammonium]-4-(2-pyridyl)-1H-1,2,3-triazolechloride (1425562-48-6) → [palladium(II) 1-(4-N,N’,N’’-trimethylbutylammonium)-4-(2-pyridyl)-1H-1,2,3-triazoledichloride]chloride (1425725-67-2)

Conditions	Yield
In methanol; dichloromethane for 1h;	100%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + tripiperidino-phosphine (13954-38-6) → dichloro{bis[1,1’,1’’-(phosphinetriyl)tripiperidine]}palladium(II) (68494-72-4, 955117-31-4)

Conditions	Yield
In toluene at 20℃; for 0.166667h;	100%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + (trimethylsilyl)methylmagnesium chloride (13170-43-9) → bis[(trimethylsilyl)methyl](1,5-cyclooctadiene)palladium(II) (225931-80-6)

Conditions	Yield
In diethyl ether at -25℃; for 1.5h; Inert atmosphere;	100%
In diethyl ether at 0℃; for 0.5h; Inert atmosphere;	72%
In diethyl ether at 0℃; for 0.333333h; Inert atmosphere;	65%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + [{Fe(κ2-dppe)(η5-C5Me5)(C≡C)PPh2}2][PF6]2 → [{[Fe(κ2-dppe)(η5-C5Me5)(C≡CPPh2)]Pd(μ-Cl)Cl}2][PF6]2

Conditions	Yield
In dichloromethane at 20℃; for 1h; Inert atmosphere; Schlenk technique;	100%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + [{Fe(κ2-dppe)(η5-C5Me5)(C≡C)PPh2}2][PF6]2 → [trans-{Fe(κ2-dppe)(η5-C5Me5)(C≡CPPh2)}2PdCl2][PF6]2

Conditions	Yield
In dichloromethane at 20℃; for 1h; Inert atmosphere; Schlenk technique;	100%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + C18H34NP2(1-)*Tl(1+) → [(2,5-bis((di-iso-propylphosphino)methyl)pyrrole(-H))PdCl]

Conditions	Yield
In toluene for 2h; Inert atmosphere; Glovebox;	100%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 2-(diphenylphosphino)pyridine (37943-90-1) → bis(diphenyl-2-pyridylphosphine)palladium(II) dichloride (78088-45-6, 38255-46-8, 84773-43-3, 1246525-11-0)

Conditions	Yield
In dichloromethane N2 atm., 20°C, 45 min;	99%
In dichloromethane (Schlenk, N2) phosphine was added to a soln. of complex in CH2Cl2, the mixt. was stirred for 30 min; reduced in vol. in vac., diethyl ether was added, the solid was filtered, washed with diethyl ether and dried in vac.; elem. anal.;	91%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + (PPh2N(Me))2CO (125655-26-7) → [{Ph2PN(Me)}2CO]PdCl2 (263552-27-8)

Conditions	Yield
	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 2,6-bis(1-mesityl-1H-imidazol-3-ium-3-yl)pyridine dibromide → ((2,6-bis[3-(mesityl)imidazol-2-ylidene]pyridine)(chloro)palladium) chloride

Conditions	Yield
In tetrahydrofuran THF soln. ligand was added dropwise to cold (-50°C) soln. Pd(cod)Cl2 in THF, allowed to warm to room temp. and stirred fir 6 h; volatiles were evapd. under vac., residue was washed with petroleum and dried in vacuo;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 2,6-bis(3-(2,6-diisopropylphenyl)imidazolium)pyridine dibromide → ((2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine)(chloro)palladium) chloride

Conditions	Yield
In tetrahydrofuran THF soln. ligand was added dropwise to cold (-50°C) soln. Pd(cod)Cl2 in THF, allowed to warm to room temp. and stirred fir 6 h; volatiles were evapd. under vac., residue was washed with petroleum and dried in vacuo;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 1'-(diphenylphosphinomethyl)-2,5-dicyclohexyl-1-phosphaferrocene (803740-05-8) → dichloro[1'-(diphenylphosphinomethyl)-2,5-dicyclohexyl-1-phosphaferrocene]palladium(II) (803739-90-4)

Conditions	Yield
In dichloromethane byproducts: cod; (N2 or Ar); using Schlenk techniques; stirring of equimolar mixt. of PdCl2(cod) and (PPh2CH2C5H4)Fe(C4H2PCy2) in CH2Cl2 for 30 min at room temp.; removal of all volatiles under reduced pressure, dissolving in min. amt.of CH2Cl2; recrystn. by slow diffusion of pentane into the CH2Cl2 soln. at room temp.; elem. anal.;	99%
In chloroform-d1 (N2 or Ar); using Schlenk techniques; treatment of (PPh2CH2C5H4)Fe(C4H2PCy)2 with an equimolar of PdCl2(cod) in CDCl2; monitoring by NMR;

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 1'-[2-(diphenylphosphino)ethyl]-2,5-dicyclohexyl-1-phosphaferrocene (803740-07-0) → dichloro[1'-[2-(diphenylphosphino)ethyl]-2,5-dicyclohexyl-1-phosphaferrocene]palladium(II) (803739-95-9)

Conditions	Yield
In dichloromethane byproducts: cod; (N2 or Ar); using Schlenk techniques; stirring of equimolar mixt. of PdCl2(cod) and (PPh2CH2CH2C5H4)Fe(C4H2PCy2) in CH2Cl2 for 30 min at room temp.; removal of all volatiles under reduced pressure, dissolving in min. amt.of CH2Cl2; recrystn. by slow diffusion of pentane into the CH2Cl2 soln. at room temp.; elem. anal.;	99%
In chloroform-d1 byproducts: cod; (N2 or Ar); using Schlenk techniques; treatment of (PPh2CH2CH2C5H4)Fe(C4H2PCy)2 (PP2) with PdCl2(cod) (6) in CDCl2 at molar ratio (PP2/6=1) at room temp.; monitoring by NMR;

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + tripiperidino-phosphine (13954-38-6) → dicloro(bis(1,1',1''-(phosphinetriyl)tripiperidine))palladium (955117-31-4, 68494-72-4)

Conditions	Yield
In toluene two equivalents of phosphine-compd. added to Pd-compd. in toluene under N2 at room temp.;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + (α,α'-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]-o-xylene) disilver dichloride → dichloro(α,α'-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]-o-xylene)palladium

Conditions	Yield
In dichloromethane soln. silver carbene complex and (cod)PdCl2 in CH2Cl2 was stirred at room temp. for 24 h; elem. anal.;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + C348H276N27O18P21S6 → C348H276Cl24N27O18P21Pd12S6

Conditions	Yield
In dichloromethane a soln. in CH2Cl2 was stirred for 3 h at room temp. (Ar); evapd. to dryness, washed with THF-pentane, dried in vac.; elem. anal.;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + diethyl ether (60-29-7) + 2,6-bis(3-mesitylimidazolin-2-ylidene)pyridine disilver dichloride → ((2,6-bis[3-(mesityl)imidazol-2-ylidene]pyridine)(chloro)palladium) silver dichloride

Conditions	Yield
In dichloromethane CH2Cl2soln. silver carbene complex was added dropwise to soln.(cod)PdCl2in CH2Cl2 and stirred at room temp. for 24 h; react. mixt. was filtered, solvent was removed under vac., residue was washed with Et2O, and recrystd. from CH2Cl2/Et2O; elem. anal.;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 2,6-bis(3-(2,6-diisopropylphenyl)imidazolin-2-ylidene)pyridine disilver dichloride → ((2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine)(chloro)palladium) chloride/(silver dichloride) salt

Conditions	Yield
In dichloromethane CH2Cl2soln. silver carbene complex was added dropwise to soln.(cod)PdCl2in CH2Cl2 and stirred at room temp. for 24 h; elem. anal.;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 2,6-bis(3-mesitylimidazolin-2-ylidene)lutidine disilver dichloride → ((α,α-bis[3-(mesityl)imidazol-2-ylidene]lutidine)(chloro)palladium) chloride/(silver dichloride) salt

Conditions	Yield
In dichloromethane CH2Cl2soln. silver carbene complex was added dropwise to soln.(cod)PdCl2in CH2Cl2 and stirred at room temp. for 24 h; elem. anal.;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 2,6-bis(3-(2,6-diisopropylphenyl)imidazolin-2-ylidene)lutidine disilver dichloride → ((α,α-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]lutidine)(chloro)palladium) chloride/(silver dichloride) salt

Conditions	Yield
In dichloromethane CH2Cl2soln. silver carbene complex was added dropwise to soln.(cod)PdCl2in CH2Cl2 and stirred at room temp. for 24 h; elem. anal.;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + benzyldiisopropylphosphine (257870-28-3) → [Pd(benzyldiisopropylphosphine)2Cl2] (1013428-49-3, 675140-26-8)

Conditions	Yield
In tetrahydrofuran (N2); glovebox and Schlenk technique; P ligand (2 equiv.) was added to soln. of Pd compd. in THF; stirred at room temp. for 5 min; filtered through cotton pad; solvent removed (vac.); washed (pentane); dried (vac.); elem. anal.;	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 1,1',2,3-tetrakis(diphenylphosphino)ferrocene (259660-21-4) → [Pd2Cl4(1,1',2,3-tetrakis(diphenylphosphino)ferrocene)] (1013935-14-2)

Conditions	Yield
In chloroform (Ar); Schlenk technique; Pd complex (2 equiv.) was added to soln. of Fe complex (1 equiv.) in CHCl3 at room temp.; stirred for 3 h; evapd.; crystd. (CHCl3); elem. anal.;	99%

Upstream product

• 26764-39-6 palladium(II) chloride benzonitrile complex 
• 5259-72-3 cyclo-octa-1,5-diene 
• 57811-65-1 bis(cyclo-octa-1,5-diene)palladium 
• 79-38-9 Chlorotrifluoroethylene 
• 7647-01-0 hydrogenchloride 
• 186340-28-3 [PdCl(Et)(1,5-cyclooctadiene)] 
• 1552-12-1 1,5-cis,cis-cyclooctadiene 
• 7647-14-5 sodium chloride 
• 46059-16-9 Pd(C₉H₁₄)Cl₂ 
• 7782-50-5 chlorine 
• 7440-05-3 palladium 
• 15617-18-2 bis(benzonitrile)palladium(II) dichloride 
• 1042309-89-6 [Pd(acetonyl)Cl(1,5-cyclooctadiene)] 
• 865-49-6 chloroform-d1 

Downstream Products

• 7440-05-3 palladium 
• 12080-32-9 dichloro( 1,5-cyclooctadiene)platinum(ll) 
• 53761-88-9 [Pd2(μ-Cl)2((4,5-η-κC(1))-(C8H12C6H5))2] 
• 13965-03-2 bis-triphenylphosphine-palladium(II) chloride 
• 83095-83-4 [platinum(II)dichloride(1,2-bis(diphenylphosphino)ethane)] 
• 19978-61-1 (1,2-bis(diphenylphosphanyl)ethane)dichloridopalladium(II) 
• 514847-65-5 [PdCl2(η2-Ph2P((OC10H6)(μ-CH2)(C10H6O))PPh2-κP,κP)] 
• 219563-59-4 [PdCl(2-(2-Ph₂PC₆H₄)NCHC₆H₄O)] 
• 113778-29-3 {bis(pentafluorophenyl)platinum(μ-Cl)2palladium(η4-1,5-cyclooctadiene)} 
• 59831-02-6 bis(diphenylphosphino)propanepalladium(II) dichloride 
• 72287-26-4 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 
• 29964-62-3 [1,4-bis(diphenylphosphino)butane] palladium(ll) dichloride 
• 125897-55-4 Pd(1,5-cyclooctadiene)Cl(Te(p-phenetyl)) 
• 125897-59-8 Pd(1,5-cyclooctadiene)(Te(phenetyl))2 

Relevant articles and documents

Dual application of Pd nanoparticles supported on mesoporous silica SBA-15 and MSU-2: Supported catalysts for C-C coupling reactions and cytotoxic agents against human cancer cell lines

Two different mesoporous silica-based materials (SBA-15 and MSU-2) have been treated under mild conditions with different quantities of [PdCl2(cod)] (cod = 1,5-cyclooctadiene) to promote the formation of supported palladium nanoparticles (materials of the type SBA-15-Pd and MSU-2-Pd). The synthesized materials have been characterized by different techniques observing that the palladium nanoparticles remain impregnated in the silica. The catalytic activity of the hybrid Pd-silica materials has been tested in Suzuki-Miyaura C-C coupling reactions observing moderate conversion rates in the reactions of 3-bromoanisole with 4-carboxyphenylboronic acid and 2-bromopyridine with 4-carboxyphenylboronic acid. In addition, the synthesized materials showed a good degree of recyclability, being catalytically active in five consecutive catalytic tests. Finally, in order to evaluate the cytotoxicity of the synthesized materials, in vitro tests against five different human cancer cell lines have been carried out, observing high cytotoxic activities of the hybrid systems comparable if not somewhat higher to other systems based on metal complexes supported on mesoporous silicas described previously in the literature. To the best of our knowledge the cytotoxic study reported here represents the first evaluation of the anticancer action of supported palladium nanoparticles in human cancer cells.

Method for in-situ preparation of (1, 5-cyclooctadiene) palladium dichloride

The invention relates to a method for in-situ preparation of (1, 5-cyclooctadiene) palladium dichloride, and belongs to the technical field of preparation of noble metal homogeneous catalysts. According to the (1, 5-cyclooctadiene) palladium dichloride prepared by the in-situ method disclosed by the invention, the raw material is palladium powder, and the cost of the raw material is relatively low. Solvents and medicines used in the preparation process are conventional acid-base and alcohol solvents, so that the toxicity is low, the price is low, and the method is suitable for industrial large-scale production. Meanwhile, by adding the complexing accelerant, the use amount of the ligand 1, 5-cyclooctadiene can be effectively reduced, the cost is reduced, and meanwhile, the green and environment-friendly requirements are better met. In addition, high-temperature heating is not needed in the preparation process, reaction conditions are easy to achieve, steps are simple and convenient, the product yield is high, washing is easy, and multiple synthesis steps are directly prepared through a one-pot series connection method. And the product has the characteristics of low metal impurity content and the like, meets the use requirements of the homogeneous catalyst, and is suitable for being used as the homogeneous catalyst in the organic synthesis reaction of various medicines and fine chemical products.

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