14872-20-9

Usage

Uses

Used in Organic Synthesis:
DICHLOROBIS(PYRIDINE)PALLADIUM(II) is used as a catalyst for facilitating C-C cross-coupling reactions and carbonylation reactions in organic chemistry. Its application is crucial for the synthesis of complex organic molecules with high selectivity and efficiency, making it a valuable reagent in both chemical research and industrial processes.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, DICHLOROBIS(PYRIDINE)PALLADIUM(II) is utilized as a catalyst in the synthesis of various pharmaceutical compounds. Its ability to promote efficient and selective reactions contributes to the development of new drugs and the improvement of existing ones.
Used in Chemical Research:
DICHLOROBIS(PYRIDINE)PALLADIUM(II) is employed as a catalyst in chemical research to explore novel reaction pathways and develop new synthetic methods. Its versatility and reactivity make it an essential tool for advancing the understanding of organic chemistry and discovering innovative applications.
Used in Industrial Processes:
In industrial processes, DICHLOROBIS(PYRIDINE)PALLADIUM(II) is used as a catalyst to improve the efficiency and selectivity of chemical reactions involved in the production of various chemicals, materials, and intermediates. Its high stability and reactivity ensure consistent performance and reliability in large-scale manufacturing operations.

InChI:InChI=1/2C5H5N.2ClH.Pd/c2*1-2-4-6-5-3-1;;;/h2*1-5H;2*1H;/q;;;;+2/p-2

Upstream product

• 110-86-1 pyridine 
• 40691-28-9 PdCl₂(P(C₆H₅)(2-C₆H₄Cl)2)2 
• 1121-60-4 pyridine-2-carbaldehyde 
• 7440-05-3 palladium 
• 935544-87-9 HCN(CH₂C(O)NHC₆H₅)CHCHN(CH₂C(O)NHC₆H₅)⁽¹⁺⁾*Cl^(1-)=(HCN(CH₂C(O)NHC₆H₅)CHCHN(CH₂C(O)NHC₆H₅))Cl 
• 13750-62-4 N-benzyl-2-methylimidazole 
• 78-95-5 chloroacetone 
• 78610-10-3 Pd₂Cl₄(As(C(CH₃)3)3)2 
• 59245-57-7 tetrapyridine palladium (II) tetrachloropalladate (II) 
• 100898-99-5 bis(μ-chloro)bis[1-3-η3-(1-chloromethyl)-1-buten-3-yl]dipalladium(II) 

Downstream Products

• 632326-76-2 cis-[Pd(CH₂Ph)2(pyridine)2] 
• 6894-19-5 bis(aniline)dichloridopalladium(II) 
• 54845-69-1 cis-[Pd(C₆F₅)2(py)2] 
• 13815-17-3 tetramminepalladium(II) chloride 
• 134625-37-9 PdCl₂(PPh₃)(py) 

Relevant academic research and scientific papers

Synthesis and characterization of novel PEPPSI type bicyclic (alkyl)(amino)carbene (BICAAC)-Pd complexes

A series of bicyclic alkylamino carbenes (BICAAC) (where N-aryl = dipp, mes, 2,6-dimethyl-4-(dimethylamino)phenyl, 5a–d) and their novel air- and moisture-resistant pyridine (pyridine, 4-dimethylaminopyridine) containing palladium Pd(II) complexes (6a–e) were synthetized and characterized. As novel examples of the PEPPSI (“pyridine enhanced precatalyst preparation stabilization and initiation”)-Pd compounds, the reported complexes have shown high activity in Mizoroki–Heck coupling reaction even at as low as 100 ppm loading (TON up to 10000). Kinetic studies revealed that reactions carried out in the presence of elemental mercury resulted decrease in activity. It indicates that the coupling reaction may have both molecular and Pd(0)-mediated catalytic paths.

Bis(CBT)palladium(II) Derivatives (CBT = m-carborane-1-thiolate): Synthesis, Molecular Structure, and Physicochemical Properties of cis-[(bipy)Pd(CBT)2] and trans-[(py)2Pd(CBT)2]

The new synthesized PdII complex cis-[(bipy)Pd(CBT)2] (bipy = 2,2′-bipyridyl; CBT = m-carborane-1-thiolate anion), which is a potential BNCT (boron neutron capture therapy) agent and of structure elucidated by single-crystal X-ray work, has been studied by infrared (IR) and ultraviolet-visible light (UV-vis) spectra and its properties compared with those of the previously reported and also the structurally characterized analogue trans-[(py)2Pd(CBT)2]. This trans species, prepared via a direct method, was previously isolated from a pyridine solution, consequent to the occurring releasing of the external Pd(CBT)2 moieties of the porphyrazine macrocycle [{Pd(CBT)2}4LZn]·xH2O (L = tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazinato anion), which is an active photosensitizer in photodynamic therapy (PDT) and a potential bimodal PDT/BNCT agent. The UV-vis spectral behavior of both cis and trans species in CHCl3 solution and in the gas phase has been examined in detail by density functional theory (DFT) and time-dependent density functional theory (TDDFT) studies devoted to explain their distinct behavior observed in the region of 400-500 nm, as determined by the presence in the cis structure of a vicinal arrangement of the two CBT groups, an ensemble of results closely similar to those observed for the macrocycles [{Pd(CBT)2}4LM]·xH2O (M = MgII(H2O), ZnII, PdII). It has also been experimentally proved the tendency of the cis isomer in CHCl3/pyridine solution to be changed to the respective trans analogue, with conversion occurring in two steps, as interpreted by detailed DFT studies.

Understanding existing and designing novel synthetic routes to Pd-PEPPSI-NHC and Pd-PEPPSI-PR3pre-catalysts

The reaction mechanism leading to the formation of cross-coupling palladium pre-catalysts of the PEPPSI family was investigated. Two intermediates were isolated and proved to be both suitable synthons to the pre-catalysts, with one permitting the design of a novel and greener user-friendly synthetic route. In light of this mechanistic understanding, the traditional one-pot method was shown to be possible using stoichiometric amounts of throw-away ligand, which represents a considerable synthetic improvement over the wasteful “in pyridine” approach.

An efficient Pd(II)-(2-aminonicotinaldehyde) complex as complementary catalyst for the Suzuki-Miyaura coupling in water

An efficient new Pd(II)-(2-aminonicotinaldehyde)-catalyzed Suzuki-Miyaura coupling of the aryl halides (Br, Cl and I) and organoboronic acids at moderate temperature in water is described. Low catalyst loading, easy accessibility, being an air-stable catalyst, functional group compatibility, and water as the reaction medium are some of the key features of this synthetic method. This protocol is also applicable for gram scale.

Synthesis and catalytic application of Pd complex catalysts: Atom-efficient cross-coupling of triarylbismuthines with haloarenes and acid chlorides under mild conditions

Palladium-catalysed cross-coupling reactions are some of the most frequently used synthetic tools for the construction of new carbon–carbon bonds in organic synthesis. In the work presented, Pd(II) complex catalysts were synthesized from palladium chloride and nitrogen donor ligands as the precursors. Infrared and 1H NMR spectroscopic analyses showed that the palladium complexes were formed in the bidentate mode to the palladium centre. The resultant Pd(II) complexes were tested as catalysts for the coupling of organobismuth(III) compounds with aryl and acid halides leading to excellent yields with high turnover frequency values. The catalysts were stable under the reaction conditions and no degradation was noticed even at 150°C for one of the catalysts. The reaction proceeds via an aryl palladium complex formed by transmetallation reaction between catalyst and Ar3Bi. The whole synthetic transformation has high atom economy as all three aryl groups attached to bismuth are efficiently transferred to the electrophilic partner.

Application of Pd(II) Complexes with Pyridines as Catalysts for the Reduction of Aromatic Nitro Compounds by CO/H2O

Many efforts have been undertaken to minimize the cost of large-scale conversion of aromatic nitro compounds to amines. Toward this end, application of CO/H2O as a reducing agent instead of molecular hydrogen seems to be a promising method, and the process can be catalyzed by Pd(II) complexes. In this work, the catalytic activity of square planar complexes of general structure PdCl2(XnPy)2 (where XnPy = pyridine derivative) was studied. Particular attention was paid to the effects of substituents both in the aromatic ring of XnPy (ligand) and the nitro compound to be reduced (YC6H4NO2). Incorporation of electron-withdrawing Y in the aromatic ring of YC6H4NO2 increases the conversion, indicating that the kinetics of this process is similar to that for the carbonylation of nitrobeznene by CO in the absence of water (described in J. Mol. Catal. A: Chem. 2011, 337, 9-16). Surprisingly, the incorporation of electron-withdrawing substituents into the aromatic ring of the XnPy ligand also increases the conversion of YC6H4NO2 (regardless of the structure of the YC6H4NO2 substrate).

One pot synthesis of ureas and carbamates via oxidative carbonylation of aniline-type substrates by CO/O2 mixture catalyzed by Pd-complexes

Abstract Carbonylation of aromatic amines by direct insertion of carbon monoxide is catalyzed by PdCl2(XnPy)2 complexes (where Py = pyridine, X = -CH3, -Cl; n = 0-2) and gives, depending on the conditions, ethyl N-phenylcarbamates or N,N′-diphenylureas. For carbonylation of aniline, a proper choice of XnPy ligands in PdCl2(XnPy)2 catalyst and application of molecular oxygen instead of nitrobenzene (conventionally used oxidant for carbonylations) allow to carry out the process under mild conditions with high yield and selectivity. The best results (75% yield of the main product with selectivity of catalyst above 90%) were obtained for the process catalyzed by PdCl2(2,4-Cl2Py)2 complex at 100°C and they were greatly improved in comparison to 41% yield and 68% selectivity obtained for CO/nitrobenzene used at 180°C.

Tuning of the catalytic properties of PdCl2(X nPy)2 complexes by variation of the basicity of aromatic ligands

The position and number of substituents in pyridine ligands (X nPy) were correlated with structural, physical, and chemical properties of PdCl2(XnPy)2 complexes applied as catalysts for the carbonylation of aromatic nitrocompounds (phosgene-free method of carbamates production). Thermal stability and catalytic activity of PdCl2(XnPy)2 complexes without steric hindrance increases with increasing XnPy's basicity whereas a decrease of thermal stability and catalytic activity of the complexes is observed for sterically crowded complexes (with the ortho-substituted XnPy). The complexes with X = Cl in meta- position of XnPy decompose to a mixture of PdCl2 and metallic Pd (similarly to complexes with Me nPy) whereas complexes with ortho-chlorine (in XnPy) decompose to the organopalladium products. Therefore, two different mechanisms of thermal decomposition are proposed for PdCl2(Cl nPy)2 and PdCl2(MenPy)2. The results of complex thermal and structural analysis of a series of PdCl 2(XnPy)2 complexes allow us to get insight into the mechanism of nitrobenzene (NB) carbonylation catalyzed by PdCl 2(XnPy)2 at 150-180 °C. We conclude that the electron transfer from Pd(0) to nitrobenzene is the rate determining step of catalytic cycle of NB carbonylation.

Zwitterionic palladium complexes: Room-temperature Suzuki-Miyaura cross-coupling of sterically hindered substrates in an aqueous medium

A series of new imidazolium chlorides were straightforwardly prepared from the reactions between chloroacetone and imidazole derivatives. Deprotonation of the methylene proton next to the ketone group in these salts by pyridine led to the formation of a monodentate ligand that coordinated to palladium, readily forming zwitterionic anionic palladium pyridine complexes bearing a formal positive charge on the ligand ancillary. The pyridine ligand in the zwitterionic complexes can be facilely replaced by phosphine ligands. Seven of these new complexes were successfully characterized by X-ray crystallography. The zwitterionic phosphine complexes were highly efficient in catalyzing room-temperature Suzuki-Miyaura reactions between sterically hindered aryl chlorides and arylboronic acids in an aqueous medium.

Characterization of sites of different thermodynamic affinities on the same metal center via isothermal titration calorimetry

We investigate the binding thermodynamics of a series of phosphorus ligands to a model compound, PdCl2(solv)2, where solv refers to a molecule of solvent, using isothermal titration calorimetry (ITC). ITC allows for the quantification of the equilibrium binding constant, the binding enthalpy, and the binding stoichiometry all in a single experiment. For systems in which two equivalents of ligand were able to bind to the Pd center, the binding sites on each Pd center in solution showed a different thermodynamic affinity for the same ligand. Changes in binding modes between different phosphorus ligands were due to steric bulk and poor electron-donating ability of such ligands. Our results demonstrate ligand binding was strongly enthalpy-driven due to solvent reorganization, which is the rearrangement of solvent molecules in the bulk solvent and the solvent molecules surrounding the solvated species.