Palladium Halides Research Articles

Design of a new palladium(ii) halide complex as a bio-active material: synthesis, physico-chemical studies, DFT-computations and evaluation of anti-inflammatory, antioxidant and anti-gastric damage activities.

Colorless single crystals of the zero-dimensional hybrid compound, (C6H10N2)2[PdCl6]·2H2O were acquired through the slow evaporation technique. The crystal structure was explored using SC-XRD, which demonstrates that the material crystallizes in the centrosymmetric space group P1̄ of the triclinic system. The density functional theory method at the B3LYP/Lan2mb basis set level was employed to establish the optimized geometry and vibrational frequencies of the title compound. An acceptable correspondence was observed between the results obtained through calculation and the experimental data, including the structure, and IR spectra. The optical characteristics revealed a direct band gap energy of 2.35 eV, validating the semiconductor characteristics of this new material. The results suggest strong agreement with the experimental data and validate the involvement of metal orbitals in defining the HOMO-LUMO boundary. Simultaneous TGA-DTA shows that this material remains solid up to 210 °C. Beyond these temperatures, a gradual decomposition process occurs, extending up to 440 °C and unfolding in several steps. This process entails the liberation of diverse compounds, encompassing organic molecules, and the evaporation of chlorine ions, ultimately leading to the formation of palladium oxide (PdO) as the final product. When given to rats with gastric ulcers at a dose of 100 mg kg-1, these compounds inhibit the key enzyme responsible for neutrophil infiltration as myeloperoxidase (MPO) by 38.7%. The compound also alleviates cellular damage induced by free radicals, demonstrated by a notable 48.3% decrease in thiobarbituric acid reactive substance rates (TBARS) compared to untreated rats. Additionally, these compounds bring about a substantial 30.6% reduction in the surface area of ulcers.

Palladium(II) halide complexes of N,N,S-tridentate Schiff bases: synthesis, structural studies in solution and solid state, and analysis of Hirshfeld surfaces

Palladium(II) halide complexes of N,N,S-tridentate Schiff bases: synthesis, structural studies in solution and solid state, and analysis of Hirshfeld surfaces

A novel 1-D square-pyramidal coordinated palladium (II) hybrid compounds [C9H16N2]PdX4 (X=Cl, Br) showing broadband emission, electrical properties and narrow optical band gap

Hybrid halide perovskite-like semiconductors are attractive materials for various optoelectronic applications, from photovoltaics to smart devices. Here, two new one-dimensional palladium halides, [C9H16N2]PdCl4 (1) and [C9H16N2]PdBr4 (2) showing electrical and optical properties were prepared by reaction of 2,4,6-trimethyl-m-phenyl-enediamine with PdX2 (X ​= ​Cl, Br) in the corresponding concentrated halogen acids HX.Single-crystal X-ray diffraction analysis reveals that compounds [C9H16N2]PdX4(X ​= ​Cl,Br) belong to isostructural phases and crystallize in the orthorhombic system with non-centrosymmetric space group Pmc21. The basic unit of the crystal structure in each compound is composed of an independent [PdX4]2- anion charge balanced by a [C9H16N2]2+ cation. Remarkably, the central Pd(II) atom is coordinated by five halogen atoms PdX5 forming a distorted square-pyramidal coordination geometry. These hybrid compounds present good thermal stability up to 500 ​K. The DSC and electric measurements show that no phase transition occurs in the compounds over the temperature range 300–400 ​K. Optical absorption measurements suggest that the two hybrids Pd(II)-based metal halides have a narrow optical band gap (Eg) of ∼3.26 ​eV (X ​= ​Cl) and ∼2.98 ​eV (X ​= ​Br) which makes them promising materials in optoelectronic devices. Besides, compounds exhibit broadband green emission excited by UV light at room temperature. The electrical study shows the contribution of the grain and grain boundary in the conduction of these materials and confirms the optical result where the conductivity of the compound (1) is higher than the compound (2). The variation of the conductivity of grain confirms the activation energies calculated for the two regions.

Theoretical study on the activation of C-H bond in ethane by PdX+ (X = F, Cl, Br, H, and CH3) in the gas phase.

The mechanism of C-H bond activation of ethane was catalyzed by palladium halide cations (PdX+ (X = F, Cl, Br, H, and CH3)), which was investigated using density functional theory (DFT) at B3LYP level. The reaction mechanism was taken into account in triplet and singlet spin state potential energy surfaces. For PdF+, PdCl+, and PdBr+, the high spin states were the ground states, whereas the ground states were the low spin states in PdH+ and PdCH3+. The reaction of PdF+, PdCl+, and PdBr+ with ethane occurred via a typical "two-state reactivity" mechanism. In contrast, for PdH+ and PdCH3+, the overall reaction performed on the ground state PESs in a spin-conserving manner. The crossing points between two potential energy surfaces were observed and effectively decreased the activation barrier in PdX+/C2H6 (X = F, Cl, and Br). The minimum energy crossing points (MECP) were obtained used the algorithm in Harvey method. The natural valence electron configuration calculations were analyzed by natural bond orbital. The distribution and contribution of the front molecular orbital of the initial complexes could be further understand by the density of states. The feature of the bonding evolution in the main pathways was studied using topological analysis including localized orbital locator and atoms in molecules.

Water gas shift reaction in the presence of palladium complexes with diphenyl-m-sulfophenylphosphine

A homogeneous catalytic system containing palladium(ii) halides, diphenyl-m-sulfo-phenylphosphine (or palladium halide complexes with diphenyl-m-sulfophenylphosphine) and hydrohalic acid was developed and studied in the liquid-phase water gas shift reaction. The system based on palladium bromide and hydrobromic acid in aqueous acetic acid (20–40 vol.%) showed the highest activity. The dependences of the initial reaction rate on the concentrations of reagents and catalyst components were studied, a mechanism for the process was proposed, and a kinetic model was developed and found to agree well with experimental results.

Revealing optoelectronic and transport properties of potential perovskites Cs2PdX6 (X = Cl, Br): A probe from density functional theory (DFT)

Metal-halide perovskites are rapidly emerging crystalline materials that are reasonably preferred as leading aspirant for applications in optoelectronic and thermoelectric devices. In this paper, we have thoroughly reviewed and performed calculations to reveal optoelectronic and transport properties for a potential newcomer, Cs2PdX6 (X = Cl, Br) termed as Cesium Palladium Halides (CPH). Outcome of present computations are compared with available results and a reasonable agreement is recorded. Energy band gap computations performed reveal indirect band gap of 2.29 eV for Cs2PdCl6, which substantially reduces to 1.22 eV when ‘Cl’ is replaced by ‘Br’. Optical absorption spectra investigations performed here, in the energy range from 3 to 5 eV confirms effective utilization of these compounds in solar cells and other optoelectronic applications. In addition, the transport properties computations performed using semi-classical Boltzmann theory, shows constant pattern of thermo power near ambient temperature range (200–500 K), which admits possible utilization of these compounds as low temperature thermoelectric materials. Performed ZT calculations demonstrates reasonably good thermoelectric performance for both materials, as there exist minor variation (0.1) in the values over wide temperature ranges i.e. from 100 to 800 K. Further, detailed analysis of transport properties predicts p-type semiconducting nature of the present series of materials.

Silane‐bridged diphosphine ligand for palladium‐catalyzed ethylene oligomerization

In this study, bis(diphenylphosphinemethyl)dimethyl silane (L1) and its palladium(II) halide complex, L1/PdCl2 (C1), were synthesized and characterized. Single‐crystal X‐ray analysis of the complex revealed bidentate coordination at the Pd center. In combination with methylaluminoxane (MAO) as co‐catalyst, C1 exhibited excellent catalytic activity and selectivity for ethylene dimerization toward butene. The maximum catalytic activity obtained from the C1/MAO system for ethylene dimerization to yield butenes was 7.33 × 105 g/(molPd·h). The selectivity toward butene remained stable and high (> 96%) over the various conditions.

Palladium(II)‐Catalyzed Regio‐ and Stereoselective Hydroarylation of Diphenylphosphorylallenes with Arylboronic Acids in the Presence of Sodium Hydroxide and Oxygen

AbstractThe palladium(II)‐catalyzed hydroarylation of diphenylphosphorylallenes (via 1,2‐addition of the allenic double bond) with arylboronic acids in the presence of sodium hydroxide and oxygen is developed. The regioselectivities turn out to be well controlled, affording 2‐aryl‐3‐(diphenylphosphinyl)alkenes as the only product. Moreover, the stereoselectivities for reactions of γ‐substituted allenes can also be nicely controlled, resulting in the formation of Z‐alkenes. The reaction shows high substituent loading capability and tolerance of various substituents. A mechanism, including transmetalation of arylboronic acid with palladium halides, insertion of the 1,2‐allenic double bond to the Pd−Ar bond, and protonation to afford the final hydroarylation product is proposed.magnified image

Influence of Halide Ions on Anodic Oxidation of Ethanol on Palladium

Ethanol oxidation on polycrystalline palladium electrodes in alkaline media was studied in the presence of halide ions. Addition of halide ions decreased the ethanol oxidation peak current monotonically as a function of increasing halide concentration. The extent of poisoning was found to be in the order I− > Br− > Cl−. Thus, Cl− ions show appreciable inhibition of ethanol oxidation peak current at [Cl−] ~ 10−3 M, whereas Br− and I− inhibit ethanol oxidation even at [Br−] or [I−] ~ 10−6 M. The potential of the ethanol oxidation peak shifted positive with increasing halide ion concentration. The extent of the shift was found to be in the order I− > Br− > Cl−. This study is relevant due to the widespread use of palladium halide complexes in the production of Pd electrocatalysts for ethanol oxidation and other electrocatalytic reactions.

Symmetrically and unsymmetrically substituted bis(pyrazole)-palladium(II) and nickel(II) halides as Pre-catalysts for ethylene dimerization and Friedel-Crafts alkylation of toluene and benzene

Bis(pyrazole)-palladium(II) and nickel(II) halide complexes, [(pz)2PdCl2] (1), [(3,5-Me2pz)2PdCl2] (2), [(3,5-tBu2pz)2PdCl2] (3), [(3,5-Ph2pz)2PdCl2] (4), [(3-CF3,5-Phpz)2PdCl2] (5),[(pz)4NiBr2] (6), [(3,5-Me2pz)2NiBr2] (7), [(3,5-tBu2pz)2NiBr2] (8), [(3,5-Ph2pz)2NiBr2] (9) and [(3-CF3,5-Phpz)2NiBr2] (10), were investigated as catalysts for ethylene oligomerization using four alkylaluminium compounds as co-catalysts in toluene, benzene and chlorobenzene. The palladium complexes with ethylaluminium dichloride (EtAlCl2) in toluene selectively produced ethyl- and butyl- toluenes via a Friedel-Crafts alkylation of toluene from the ethylene and butenes formed from the dimerization of ethylene. On the other hand, the nickel complexes produced a mixture of butenes and their Friedel-Crafts toluene alkylation products, but very little ethyltoluene. Changing the solvent to benzene produced similar alkyl-aromatics but in chlorobenzene the reaction produced butenes and a yellow oil, with a molecular weight between 501 to 509 g mol-1; representing C18-C20 carbon-containing compounds. Similarly changing the co-catalyst to methylaluminoxane (MAO), modified methylaluminoxane (MMAO), diethylaluminium chloride (Et2AlCl) and ethylaluminiumsesquichloride (Et3Al2Cl3) also selectively produced butenes and little or no alkylaromatics.

Synthesis and characterization of (π-allyl)palladium(II) complexes containing dialkylbiaryl phosphine ligands

Neutral (π-allyl)palladium(II) halide complexes, which are air and moisture tolerant, containing dialkylbiaryl (alkyl=cyclohexyl or t-butyl) phosphine ligands, have been synthesized and characterized by 1H, 31P, 13C NMR spectroscopy, X-ray crystallography, and elemental analysis. Exposure of the halide complexes to sodium tetrakis(3,5-bis(trifluoromethyl)tetraphenylborate) (NaB(ArF)4) yields (π-allyl)palladium(II) cations, in which coordination of the pendent lower ring of the biphenyl moiety of the dialkylbiaryl phosphine ligand occurs. These cations have been characterized by 1H, 31P, 13C NMR spectroscopy, X-ray crystallography, and elemental analysis. The cationic complexes are not fluxional on the NMR timescale and a significant interaction exists between palladium and the arene group.

Synthesis, spectroscopic characterization and density functional studies of a bis-benzimidazole derivative and of its complexes with palladium(II) halides

The 2,6-bis(benzimidazol-2′-ylthiomethyl)pyridine ( L ) ligand and its palladium(II) complexes [Pd(L)X]X (X = Cl, Br, and I) have been synthesized and characterized by spectroscopic data acquisition. The ligand ( L ) was prepared by conventional heating as well as by microwave irradiation. Microwave irradiation shows additional features, including an easy workup, a much faster reaction and higher yields. The molar conductivity data reveal that the complexes form a 1:1 electrolyte in DMSO. The geometries, ground-state energetics and vibrational spectra of ( L ) and of its complexes have been elucidated, in terms of quantum chemical calculations. In the mononuclear complexes, the palladium atom is coordinated to three nitrogen atoms and one terminal halogen atom in a slightly distorted square planar arrangement. The present elemental analyses, FT–IR (mid, far), 1 H and 13 C NMR spectra are in good accordance with the square planar geometry around the Pd ion. The thermal behaviors of the complexes have been assessed by thermal gravimetric and differential thermal analyses.

Preparation of potentially porous, chiral organometallic materials through spontaneous resolution of pincer palladium conformers

Understanding the mechanism by which advanced materials assemble is essential for the design of new materials with desired properties. Here, we report a method to form chiral, potentially porous materials through spontaneous resolution of conformers of a PCP pincer palladium complex ({2,6-bis[(di-t-butylphosphino)methyl]phenyl}palladium(II)halide). The crystallisation is controlled by weak hydrogen bonding giving rise to chiral qtz-nets and channel structures, as shown by 16 such crystal structures for X = Cl and Br with various solvents like pentane and bromobutane. The fourth ligand (in addition to the pincer ligand) on palladium plays a crucial role; the chloride and the bromide primarily form hexagonal crystals with large 1D channels, whereas the iodide (presumably due to its inferior hydrogen bonding capacity) forms monoclinic crystals without channels. The hexagonal channels are completely hydrophobic and filled with disordered solvent molecules. Upon heating, loss of the solvent occurs and the hexagonal crystals transform into other non-porous polymorphs. Also by introducing a strong acid, the crystallisation process can be directed to a different course, giving several different non-porous polymorphs. In conclusion, a number of rules can be formulated dictating the formation of hexagonal channel structures based on pincer palladium complexes. Such rules are important for a rational design of future self-assembling materials with applications in storage and molecular recognition.

Calculations of microconstants and equilibrium formation constants for platinum(II) and palladium(II) halide complexes in solution

Distribution diagrams and formation functions for halide complexes [M(H2O)4 − nCln]2 − n (M = Pt(II) or Pd(II)) and [PdCl4 − nBrn]2− (n = 0–4) in solution are analyzed in terms of the matrix model. Equilibrium constants for binding the first ligand \(\left( {\bar K} \right)\) and corrections for the mutual influence between ligands (ω) in the course of complex formation in solution are calculated. In examples analyzed, the substitution of chloride ion for water in the coordination sphere of platinum(II) and palladium(II) is an anti-cooperative process. The substitution of bromide ion for chloride ion in the coordination sphere of [PdCl4]2− is weakly cooperative. Quantum-chemical calculations show that platinum(II) and palladium(II) cis-bisaquadichloro complexes in the gas phase are thermodynamically less stable than trans-isomers. The cis-trans isomerization constants in the gas phase calculated by the DFT method and those found for solutions using the matrix model have the same order of magnitude.

Neutral Organometallic Halogen Bond Acceptors: Halogen Bonding in Complexes of PCPPdX (X = Cl, Br, I) with Iodine (I(2)), 1,4-Diiodotetrafluorobenzene (F4DIBz), and 1,4-Diiodooctafluorobutane (F8DIBu).

The behavior of a sterically crowded neutral pincer {2,6-bis[(di-t-butylphosphino)methyl]-phenyl}palladium (PCPPd) halides, PCPPdX (X = Cl, Br or I), as XB acceptors with strong halogen bond (XB) donors, iodine (I2), 1,4-diiodotetrafluorobenzene (F4DIBz), and 1,4-diiodooctafluorobutane (F8DIBu) were studied in the solid state. The co-crystallization experiments afforded high-quality single crystals of XB complexes PCPPdCl–I2 (1a), PCPPdBr–I2 (2a), PCPPdI–I2(3a), PCPPdCl–F4DIBz (1b), PCPPdBr–F4DIBz (2b), and PCPPdBr–F8DIBu (2c). The 1:1 iodine complexes (1a, 2a, and 3a) all showed a strong halogen bonding interaction, the reduction of the sum of the van der Waals radii of halogen to iodine being 24.6 (1a), 23.9 (2a), and 19.4% (3a) with X···I–I angles of 177, 176, and 179°, respectively. While the pincer palladium chloride 1 and bromide 2 were crystallographically isomorphous and showed similar XB behavior, the palladium iodide complex, 3, exhibited markedly different properties, and unlike 1 and 2 it does not, under similar conditions, result in XB complexes with the weaker XB donors F4DIBz and F8DIBu. The results indicate that PCPPdI is not nucleophilic enough to have XB interactions with other donors than iodine. However, the weaker XB donors F4DIBz and F8DIBu form XB complexes with the chloride 1 and especially with the bromide 2. The prevalence of the halogen bonding with 2 is probably not only electronic in origin, and it seems to offer the best balance between electron poorness and steric availability. The XB interactions with F4DIBz and F8DIBu are much weaker than with iodine, the reduction of the sum of the van der Waals radii of halogen to iodine being 13.5, 12.3, and 14.6% with C–I···X angles between 163 and 179° for 1b, 2b, and 2c, respectively, and results in polymeric (···1···F4DIBz···1···F4DIBz···)n, (···2···F4DIBz···2···F4DIBz···)n, and (···2···F8DIBu···2···F8DIBu···)n one-dimensional zigzag chains in the solid state.

Electrospray Ionization Mass Spectrometry of Palladium(II) Quinolinylaminophosphonate Complexes

The mass spectrometric behavior of palladium(II) halide complexes of three types of quinolinylaminophosphonates, diethyl and dibutyl esters of [α-anilino-(quinolin-2-yl)methyl]phosphonic (L1, L2), [α-anilino-(quinolin-3-yl)methyl]phosphonic (L3, L4), and [α-(quinolin-3-ylamino)-N-benzyl]phosphonic acid (L5, L6), was investigated under positive ion electrospray ionization conditions. Each type of ligand forms complexes with different metal-ligand interactions. Mononuclear dihalide adducts cis-[Pd(L1/L2)X(2)] (1-4) and trans-[Pd(L3/L4)(2)X(2)] (5-8) as well as dinuclear tetrahalide complexes [Pd(2)(L5/L6)(3)X(4)] (9-12) (X=Cl, Br) are formed by metal bonding either through the quinoline or both the quinoline and amino nitrogen atoms. The sodiated molecule [M + Na](+) is observed in the mass spectra of all the complexes, and its abundance as well as the fragmentation pathway depend on the type of the complex. In the cis complexes (1-4) the initial decomposition goes under two fragmentation routes: those in which the sodium molecular adduct sequentially loses halides HX/NaX and those in which this loss is in the competition with the loss of dialkyl phosphite. The predominant pathways for decomposition of trans dihalide (5-8) and tetrahalide (9-12) complexes include three competitive reactions; the loss of halides, dialkyl phosphites and the intact phosphonate ligand molecule and its fragments formed by ester dissociation or complete loss of the phosphonate ester moiety. A series of acetonitrile adducts and cluster ions derived from dimolecular clusters [2M + Na](+) were also detected. The most important fragmentation patterns are rationalized and supported by the MS(n) studies.

Palladium(II) complexes of quinolinylaminophosphonates: Synthesis, structural characterization, antitumor and antimicrobial activity

Three types of palladium(II) halide complexes of quinolinylaminophosphonates have been synthesized and studied. Diethyl and dibutyl [α-anilino-(quinolin-2-ylmethyl)]phosphonates ( L1, L2) act as N, N-chelate ligands through the quinoline and aniline nitrogens giving complexes cis-[Pd( L1/L2) X 2] (X═Cl, Br) ( 1–4). Their 3-substituted analogues [α-anilino-(quinolin-3-ylmethyl)]phosphonates ( L3, L4) form dihalidopalladium complexes trans-[Pd( L3/L4) 2X 2] ( 5–8), with trans N-bonded ligand molecules only through the quinoline nitrogen. Dialkyl [α-(quinolin-3-ylamino)- N-benzyl]phosphonates ( L5, L6) give tetrahalidodipalladium complexes [Pd 2( L5/L6) 3X 4] ( 9–12), containing one bridging and two terminal ligand molecules. The bridging molecule is bonded to the both palladium atoms, one through the quinoline and the other through the aminoquinoline nitrogen, whereas terminal ligand molecules are coordinated each only to one palladium via the quinoline nitrogen. Each palladium ion is also bonded to two halide ions in a trans square-planar fashion. The new complexes were identified and characterized by elemental analyses and by IR, UV–visible, 1H, 13C and 31P nuclear magnetic resonance and ESI-mass spectroscopic studies. The crystal structures of complexes 1–4 and 6 were determined by X-ray structure analysis. The antitumor activity of complexes in vitro was investigated on several human tumor cell lines and the highest activity with cell growth inhibitory effects in the low micromolar range was observed for dipalladium complexes 11 and 12 derived from dibutyl ester L6. The antimicrobial properties in vitro of ligands and their complexes were studied using a wide spectrum of bacterial and fungal strains. No specific activity was noted. Only ligands L3 and L4 and tetrahalidodipalladium complexes 9 and 11 show poor activities against some Gram positive bacteria.

Distinguishing Between Pathways for Transmetalation in Suzuki−Miyaura Reactions

We report a systematic study of the stoichiometric reactions of isolated arylpalladium hydroxo and halide complexes with arylboronic acids and aryltrihydroxyborates to evaluate the relative rates of the two reaction pathways commonly proposed to account for transmetalation in the Suzuki-Miyaura reaction. On the basis of the relative populations of the palladium and organoboron species generated under conditions common for the catalytic process and the observed rate constants for the stoichiometric reactions between the two classes of reaction components, we conclude that the reaction of a palladium hydroxo complex with boronic acid, not the reaction of a palladium halide complex with trihydroxyborate, accounts for transmetalation in catalytic Suzuki-Miyaura reactions conducted with weak base and aqueous solvent mixtures.

Oxazoles revisited: On the nature of binding of benzoxazole and 2-methylbenzoxazole with the zinc and palladium halides

A synthetic and structural (X-ray) investigation into the bonding modes of benzoxazole (box) and 2-methylbenzoxazole (Mebox) ligands with halide precursors of Zn and Pd has been undertaken to clarify earlier discrepancies concerning the nature of the bonding mode(s) of the two azoles. In four structurally characterised examples, all contain the title ligands in a κ(1)N bonding motif. Calculations at the density functional level (DFT) of theory (B3LYP) confirm the ground state stability of this class of coordination for several hypothetical Pd and Zn (gas phase) compounds. The attempt to obtain suitable crystalline material of PdCl(2)(box)(2) (i.e., 5) leads to substantial complex degradation. One minor product of this process has been identified (X-ray) as the diarylformamidinato complex C(26)H(22)N(4)O(4)Pd, presumably formed via a complex combination of the decomposition products of both free box and 5.

Macrocyclic Palladium(II) Complexes in CC Coupling Reactions: Efficient Catalysis by Controlled Temporary Release of Active Species

AbstractStabilization of palladium species against agglomeration is essential for reasonable catalytic activity in CC coupling reactions. In contrast to common methods of palladium(0) complex or particle stabilization, a new concept is introduced here: it is demonstrated that a controlled release of palladium from an inactive precatalyst provides stability, too, and leads to high catalytic activity. This paper presents surprising catalytic results for Heck and Suzuki reactions with aryl chlorides and bromides, using three highly stable macrocyclic palladium complexes as catalyst precursors. Three different behaviour patterns for the macrocyclic complexes can be deduced from the evaluation of catalytic activities, UV‐Vis spectroscopy, recycling studies of immobilized complexes, and ligand addition experiments. (i) Palladium tetraphenylporphyrin reversibly releases only extremely low amounts of palladium during the reactions, and low coupling activities are observed. (ii) Release of palladium from its phthalocyanine complex is irreversible; cumulative release of palladium into the reaction mixtures leads to high catalytic activity. (iii) Extraordinary results were obtained with a Robson‐type complex of palladium, which reversibly releases effectual amounts of palladium into solution under reaction conditions. This controlled release prevents the formation of inactive palladium agglomerates under harsh conditions and leads to high catalytic performances. Even strongly deactivated electron‐rich aryl chlorides (4‐chloroanisole) can be completely and selectively converted by the in situ formed anionic palladium halide complexes; the addition of typical stabilizing additives (TBAB) was found to be unnecessary. The bimetallic palladium complex is regenerated at the end of the reaction. These results contribute to the current understanding of the active species in CC coupling reactions of Heck and Suzuki types.