Palladium–cadmium sulfide nanopowder at oil–water interface as an effective catalyst for Suzuki–Miyaura reactions

A simple and effective strategy is described for the synthesis of Pd–CdS nanopowder by the reduction of an organopalladium(II) complex, [PdCl₂(cod)] (cod = cis ,cis ‐1,5‐cyclooctadiene), in the presence of CdS quantum dots (QDs) at a toluene–water interface. We investigated the impact of addition of CdS QDs on catalytic activity of Pd nanoparticles (NPs). The Pd–CdS nanopowder functions as an efficient catalyst for Suzuki–Miyaura reactions for the formation of carbon–carbon bonds. There is a high electron density on Pd NPs and due to their high electron affinity they behave as an electron scavenger from CdS increasing the rate of oxidative addition, which is the rate‐determining step of the catalytic cycle, and, just as we expect, the C─C coupling reaction with the Pd–CdS nanopowder is faster and occurs in less time than that with Pd nanocatalysts. Compared to classical reactions, this method consistently has the advantages of short reaction times, high yields in a green solvent, reusability of the catalyst without considerable loss of catalytic activity and low cost, and is a facile method for the preparation of the catalyst.     

Excellent Suzuki–Miyaura catalytic activity of a new Pd(II) complex with sulfonamide–Schiff base ligand

A new air‐stable Pd(II) complex containing a sulfonamide–Schiff base ligand has been synthesized, characterized and investigated as a catalyst for the Suzuki–Miyaura reactions of aryl halides with arylboronic acids. Theoretical calculations (B3LYP) and spectroscopic evidence suggest that the sulfonamide–Schiff base coordinates to the Pd centre through sulfonamide nitrogen (? SO₂NH₂) rather than imine (? CH?N). The complex shows excellent cross‐coupling activity with aryl bromides in water at room temperature and aryl chlorides in isopropanol at 60°C. Copyright © 2016 John Wiley & Sons, Ltd.     

An Efficient Low‐Temperature Stille–Migita Cross‐Coupling Reaction for Heteroaromatic Compounds by Pd–PEPPSI–IPent

The reactivity of Pd–PEPPSI (Pyridine, Enhanced, Precatalyst, Preparation, Stabilization, and Initiation) precatalysts in the Stille–Migita cross‐coupling reaction between heteroaryl stannanes and aryl or heteroaryl halides was evaluated. In general, Pd–PEPPSI–IPent (IPent=diisopentylphenylimidazolium derivative) demonstrated high efficiency over a variety of challenging aryl or heteroaryl halides with thiophene‐, furan‐, pyrrole‐, and thiazole‐based organostannanes when compared with Pd–PEPPSI–IPr (IPr=diisopropylphenylimidazolium derivative). The transformations proceeded at appreciably lower temperatures (30–80 °C) than triarylphosphine‐based Pd catalysts, improving the scope of this useful carbon–carbon bond‐forming process.     

Investigation of Suzuki–Miyaura catalyst‐transfer polycondensation of AB‐type fluorene monomer using coordination‐saturated aryl Pd(II) halide complexes as initiators

Novel triarylamine‐based coordination‐saturated aryl Pd(II) halide complexes ligated by PEt₃, PCy₃, and P(o‐tol)₃ were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors. Suzuki–Miyaura coupling polymerization of 2‐(7‐halide‐9,9‐dioctylfluoren‐2‐yl)?1,3,2‐dioxaborinane with these Pd(II) complexes as initiators was investigated for the synthesis of poly(fluorene)s with triarylamine end group. Pd(II) complexes with PCy₃ or P(o‐tol)₃ exhibited catalytic activity and realized the catalyst‐transfer polycondensation at 75 °C and room temperature, respectively, while the polymerization using Pd(II) catalyst ligated by PEt₃ did not proceed, which indicated that the bulky phosphine ligands could facilitate the reductive elimination and further promote the polymerization. In addition, the dimeric Pd(II) complex with P(o‐tol)₃ can convert into monomeric Pd(II) intermediate with an open coordination site, which had a higher activity. The end groups of the afforded polyfluorene were analyzed by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, in which the Ar/H end groups are indicative of the catalyst‐transfer polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1457–1463     

Pd(II) complexes of Schiff bases and their application as catalysts in Mizoroki–Heck and Suzuki–Miyaura cross‐coupling reactions

Schiff bases of 2‐(phenylthio)aniline, (C₆H₅)SC₆H₄N?CR (R = (o‐CH₃)(C₆H₅), (o‐OCH₃)(C₆H₅) or (o‐CF₃)(C₆H₅)), and their palladium complexes (PdLCl₂) were synthesized. The compounds were characterized using ¹H NMR and ¹³C NMR spectroscopy and micro analysis. Also, electrochemical properties of the ligands and Pd(II) complexes were investigated in dimethylformamide–LiClO₄ solution with cyclic and square wave voltammetry techniques. The Pd(II) complexes showed both reversible and quasi‐reversible processes in the ?1.5 to 0.3 V potential range. The synthesized Pd(II) complexes were evaluated as catalysts in Mizoroki–Heck and Suzuki–Miyaura cross‐coupling reactions. Copyright © 2015 John Wiley & Sons, Ltd.     

N‐heterocyclic carbene–palladium(II) complex supported on magnetic mesoporous silica for Heck cross‐coupling reaction

Magnetic mesoporous silica was prepared via embedding magnetite nanoparticles between channels of mesoporous silica (SBA‐15). The prepared composite (Fe₃O₄@SiO₂‐SBA) was then reacted with 3‐chloropropyltriethoxysilane, sodium imidazolide and 2‐bromopyridine to give 3‐(pyridin‐2‐yl)‐1H‐imidazol‐3‐iumpropyl‐functionalized Fe₃O₄@SiO₂‐SBA as a supported pincer ligand for Pd(II). The functionalized magnetic mesoporous silica was further reacted with [PdCl₂(SMe₂)₂] to produce a supported N‐heterocyclic carbene–Pd(II) complex. The obtained catalyst was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray analysis, vibrating sample magnetometry, Brunauer–Emmett–Teller surface area measurement and X‐ray diffraction. The amount of the loaded complex was 80.3 mg g^?1, as calculated through thermogravimetric analysis. The formation of the ordered mesoporous structure of SBA‐15 was confirmed using low‐angle X‐ray diffraction and transmission electron microscopy. Also, X‐ray photoelectron spectroscopy confirmed the presence of the Pd(II) complex on the magnetic support. The prepared magnetic catalyst was then effectively used in the coupling reaction of olefins with aryl halides, i.e. the Heck reaction, in the presence of a base. The reaction parameters, such as solvent, base, temperature, amount of catalyst and reactant ratio, were optimized by choosing the coupling reaction of 1‐bromonaphthalene and styrene as a model Heck reaction. N‐Methylpyrrolidone as solvent, 0.25 mol% catalyst, K₂CO₃ as base, reaction temperature of 120°C and ultrasonication of the catalyst for 10 min before use provided the best conditions for the Heck cross‐coupling reaction. The best results were observed for aryl bromides and iodides while aryl chlorides were found to be less reactive. The catalyst exhibited noticeable stability and reusability.     

Mild and Selective Catalytic Hydrogenation of the C=C Bond in α,β‐Unsaturated Carbonyl Compounds Using Supported Palladium Nanoparticles

Chemoselective reduction of the C=C bond in a variety of α,β‐unsaturated carbonyl compounds using supported palladium nanoparticles is reported. Three different heterogeneous catalysts were compared using 1 atm of H₂: 1) nano‐Pd on a metal–organic framework (MOF: Pd⁰‐MIL‐101‐NH₂(Cr)), 2) nano‐Pd on a siliceous mesocellular foam (MCF: Pd⁰‐AmP‐MCF), and 3) commercially available palladium on carbon (Pd/C). Initial studies showed that the Pd@MOF and Pd@MCF nanocatalysts were superior in activity and selectivity compared to commercial Pd/C. Both Pd⁰‐MIL‐101‐NH₂(Cr) and Pd⁰‐AmP‐MCF were capable of delivering the desired products in very short reaction times (10–90 min) with low loadings of Pd (0.5–1 mol %). Additionally, the two catalytic systems exhibited high recyclability and very low levels of metal leaching.     

Structure–activity relationship of N‐heterocyclic carbene–Pd(II)–imidazole complexes in Suzuki–Miyaura coupling between 4‐methoxyphenyl chloride and phenylboronic acid

A series of N‐heterocyclic carbene–PdCl₂–imidazole [NHC–Pd(II)–Im] complexes were synthesized and the structure of most of them was unambiguously determined by X‐ray single‐crystal diffraction. The structure–activity relationship of these complexes was investigated for the Suzuki–Miyaura coupling between 4‐methoxyphenyl chloride and phenylboronic acid, and the effect of the NHCs and Im moieties were fully discussed. The sterically hindered IPr‐based complex showed the highest catalytic activity. Copyright © 2013 John Wiley & Sons, Ltd.     

Room‐temperature Suzuki–Miyaura cross‐coupling reaction with α‐diimine Pd(II) catalysts

An α‐diimine Pd(II) complex containing chiral sec‐phenethyl groups, {bis[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐2,3‐butadiene}dichloropalladium (rac‐ C1 ), was synthesized and characterized. rac‐ C1 was applied as an efficient catalyst for the Suzuki–Miyaura cross‐coupling reaction between various aniline halides and arylboronic acid in PEG‐400–H₂O at room temperature. Among a series of aniline halides, rac‐ C1 did not catalyze the cross‐coupling of aniline chlorides and fluorides but efficiently catalyzed the cross‐coupling of aniline bromides and iodides with phenylboronic acid. The catalytic activity reduced slightly with increasing steric hindrance of the aniline bromides. The complexes {bis[N,N′‐(4‐fluoro‐2,6‐diphenylphenyl)imino]‐2,3‐butadiene}dichloropalladium and {bis[N,N′‐(4‐fluoro‐2,6‐diphenylphenyl)imino]acenaphthene}dichloropalladium were also found to be efficient catalysts for the reaction. Copyright © 2015 John Wiley & Sons, Ltd.     

The first stereospecific arylation of (Z)‐germyl(stannyl)ethenes with an aryl halide or heteroaryl halide under palladium‐catalysis

A combination catalyst of Pd(dba)₂‐PPh₃‐CuI‐LiCl or Pd(dba)₂‐P(2‐furyl)₃‐CuI‐LiCl effectively catalyzed the cross‐coupling of (Z)‐germyl(stannyl)ethenes with aryl halides, providing novel triethyl(2,2‐diarylethenyl)germanes in good to high yields. The reaction proceeds with retention of configuration. Cross‐coupling results in the formation of phenylene or phenyleneethynylene derivatives with terminal stereochemically defined vinylgermane unit(s). Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis of a palladium complex bearing 2‐phenylbenzothiazole and its application to Suzuki–Miyaura coupling reaction

The palladacycle complex [L^sPdOAc]₂ bearing 2‐phenyl benzothiazole was synthesized and characterized by NMR and X‐ray crystallography. [L^sPdOAc]₂ was used as a catalyst in the Suzuki–Miyaura cross coupling reaction of 4‐bromotoluene with phenylboronic acid, which resulted in a conversion of >90% with 5 mol% of the Pd complex within 10 min at 60°C.     

Synthesis of peroxide‐curable butyl rubber via suzuki–miyaura coupling of halogenated butyl rubber with 4‐vinylphenylboronic acid

The Suzuki–Miyaura coupling reaction of brominated butyl rubber (BIIR) and/or chlorinated butyl rubber with a mixture of 4‐vinylphenylboronic acid and phenylboronic acid was carried out in THF under various conditions using a di‐μ‐chlorobis [5‐hydroxy‐2‐[1‐(hydroxyimino‐κN)ethyl]phenylκC] palladium(II) dimer, which is a type of cyclopalladated complex, as a catalyst. When BIIR and a small amount (Pd/Br ≈ 1/1000) of complex were used as the substrate and catalyst, respectively, a 4‐vinylphenyl and phenyl group could be introduced to butyl rubber in a high yield. Isomerization of the exo carbon–carbon double bond in BIIR was observed during the coupling reaction to give a cis and trans endo structure. The peroxide curing behavior of the resulting polymer at 170 °C indicated that the polymer could be cured by dicumyl peroxide, and the maximum torque of the resulting material, which reflects the crosslink density, was controllable by the composition of the boronic acids used. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Mechanistic Investigation of Catalyst‐Transfer Suzuki–Miyaura Condensation Polymerization of Thiophene–Pyridine Biaryl Monomers with the Aid of Model Reactions

We have investigated the requirements for efficient Pd‐catalyzed Suzuki–Miyaura catalyst‐transfer condensation polymerization (Pd‐CTCP) reactions of 2‐alkoxypropyl‐6‐(5‐bromothiophen‐2‐yl)‐3‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)pyridine ( 12 ) as a donor–acceptor (D –A) biaryl monomer. As model reactions, we first carried out the Suzuki–Miyaura coupling reaction of X–Py–Th–X′ (Th=thiophene, Py=pyridine, X, X′=Br or I) 1 with phenylboronic acid ester 2 by using tBu₃PPd⁰ as the catalyst. Monosubstitution with a phenyl group at Th‐I mainly took place in the reaction of Br–Py–Th–I ( 1 b ) with 2 , whereas disubstitution selectively occurred in the reaction of I–Py–Th–Br ( 1 c ) with 2 , indicating that the Pd catalyst is intramolecularly transferred from acceptor Py to donor Th. Therefore, we synthesized monomer 12 by introduction of a boronate moiety and bromine into Py and Th, respectively. However, examination of the relationship between monomer conversion and the M_n of the obtained polymer, as well as the matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectra, indicated that Suzuki–Miyaura coupling polymerization of 12 with (o‐tolyl)tBu₃PPdBr initiator 13 proceeded in a step‐growth polymerization manner through intermolecular transfer of the Pd catalyst. To understand the discrepancy between the model reactions and polymerization reaction, Suzuki–Miyaura coupling reactions of 1 c with thiopheneboronic acid ester instead of 2 were carried out. This resulted in a decrease of the disubstitution product. Therefore, step‐growth polymerization appears to be due to intermolecular transfer of the Pd catalyst from Th after reductive elimination of the Th‐Pd‐Py complex formed by transmetalation of polymer Th–Br with (Pin)B–Py–Th–Br monomer 12 (Pin=pinacol). Catalysts with similar stabilization energies of metal–arene η²‐coordination for D and A monomers may be needed for CTCP reactions of biaryl D–A monomers.     

Structural studies on aryl‐substituted enaminoketones and their thio analogues. Part II. Experimental and DFT calculated carbon–carbon coupling constants,nJ(CC)'s (n = 1–3)

Spin–spin carbon–carbon coupling constants across one, two and three bonds, J(CC), have been measured for a series of aryl‐substituted Z‐s‐Z‐s‐E enaminoketones and their thio analogues. As a result, a large set, altogether 178, of J(CC)s has been obtained. It consists of 82 couplings across one bond, 31 couplings across two bonds and 65 couplings across three bonds. Independently, the DFT calculations at the B3PW91/6‐311++G(d,p)//B3PW91/6‐311++G(d,p) level yielded a set of theoretical J(CC) values. A comparison of these two sets of data gave an excellent linear correlation with parameters a and b close to ideal; a = 0.9978 which is not far from unity and b = 0.22 Hz which is close to zero. The ¹J(CC) couplings determined for the crucial fragment of the molecules, i.e. ? C?C? C?O (or ? C?C? C?S), are: ¹J(C?C) ≈ 68 Hz (67 Hz) and ¹J(C? C) = 60.5 Hz (60.0 Hz). The corresponding couplings found for the Z‐s‐Z‐s‐E isomer of the parent enaminoketone, 4‐methylamino‐but‐3‐en‐2‐one are 64.1 and 59.3 Hz, respectively. The most sensitive towards substitution of the oxygen atom by sulfur are two‐bond couplings between the α‐vinylic and aromatic C_ipso carbon atoms, which attain 12 Hz in the enaminoketone derivatives and decrease to 5 Hz in their thio analogues. Copyright © 2009 John Wiley & Sons, Ltd.     

Crystal structures of the pyrazinamide–p‐aminobenzoic acid (1/1) cocrystal and the transamidation reaction product 4‐(pyrazine‐2‐carboxamido)benzoic acid in the molten state

The synthesis of pharmaceutical cocrystals is a strategy to enhance the performance of active pharmaceutical ingredients (APIs) without affecting their therapeutic efficiency. The 1:1 pharmaceutical cocrystal of the antituberculosis drug pyrazinamide (PZA) and the cocrystal former p‐aminobenzoic acid (p‐ABA), C₇H₇NO₂·C₅H₅N₃O, (1), was synthesized successfully and characterized by relevant solid‐state characterization methods. The cocrystal crystallizes in the monoclinic space group P2₁/n containing one molecule of each component. Both molecules associate via intermolecular O—H...O and N—H...O hydrogen bonds [O...O = 2.6102 (15) Å and O—H...O = 168.3 (19)°; N...O = 2.9259 (18) Å and N—H...O = 167.7 (16)°] to generate a dimeric acid–amide synthon. Neighbouring dimers are linked centrosymmetrically through N—H...O interactions [N...O = 3.1201 (18) Å and N—H...O = 136.9 (14)°] to form a tetrameric assembly supplemented by C—H...N interactions [C...N = 3.5277 (19) Å and C—H...N = 147°]. Linking of these tetrameric assemblies through N—H...O [N...O = 3.3026 (19) Å and N—H...O = 143.1 (17)°], N—H...N [N...N = 3.221 (2) Å and N—H...N = 177.9 (17)°] and C—H...O [C...O = 3.5354 (18) Å and C—H...O = 152°] interactions creates the two‐dimensional packing. Recrystallization of the cocrystals from the molten state revealed the formation of 4‐(pyrazine‐2‐carboxamido)benzoic acid, C₁₂H₉N₃O₃, (2), through a transamidation reaction between PZA and p‐ABA. Carboxamide (2) crystallizes in the triclinic space group P with one molecule in the asymmetric unit. Molecules of (2) form a centrosymmetric dimeric homosynthon through an acid–acid O—H...O hydrogen bond [O...O = 2.666 (3) Å and O—H...O = 178 (4)°]. Neighbouring assemblies are connected centrosymmetrically via a C—H...N interaction [C...N = 3.365 (3) Å and C—H...N = 142°] engaging the pyrazine groups to generate a linear chain. Adjacent chains are connected loosely via C—H...O interactions [C...O = 3.212 (3) Å and C—H...O = 149°] to generate a two‐dimensional sheet structure. Closely associated two‐dimensional sheets in both compounds are stacked via aromatic π‐stacking interactions engaging the pyrazine and benzene rings to create a three‐dimensional multi‐stack structure.     

Pd nanoparticles immobilized on PNIPAM–halloysite: highly active and reusable catalyst for Suzuki–Miyaura coupling reactions in water

Poly(N‐isopropylacrylamide)–halloysite (PNIPAM‐HNT) nanocomposites exhibited inverse temperature solubility with a lower critical solution temperature (LCST) in water. Palladium (Pd) nanoparticles were anchored on PNIPAM‐HNT nanocomposites with various amounts of HNT from 5 to 30 wt%. These Pd catalysts exhibited excellent reactivities for Suzuki–Miyaura coupling reactions at 50–70 °C in water. In particular, Pd anchored PNIPAM/HNT (95:5 w/w ratio) nanocomposites showed excellent recyclability up to 10 times in 96% average yield by simple filtration. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and characterizations of arsine– and stibine–ligated Schiff base palladacycles and their applications in Suzuki–Miyaura cross‐coupling reactions

A series of arsine‐ and stibine‐ligated Schiff base palladacycles were synthesized by the reaction of μ‐Cl‐bridged Schiff base palladacycles [Pd(C₆H₄CH]NC₆H₂R)(μ‐Cl)]₂ (R = 2,4,6‐trimethyl or 2,6‐diisopropyl) with AsPh₃ or SbPh_3. The new arsine‐ and stibine‐ligated palladacycles were fully characterized using ¹H NMR, ¹³C NMR and infrared spectroscopies, high‐resolution mass spectrometry, elemental analysis and single‐crystal X‐ray diffraction. Further exploration of the catalytic application of the palladacycles for Suzuki–Miyaura cross‐coupling reactions of aryl bromides with arylboronic acids was carried out. It was found that the new palladacycles are considerably active for these coupling reactions. Copyright © 2016 John Wiley & Sons, Ltd.     

C–C bridged Ni(II) complexes bearing β‐keto‐9‐fluorenyliminato ligands prepared by different in situ bonding mechanisms and their use in catalytic (co)polymerization of norbornene and styrene

Two C–C bridged Ni(II) complexes bearing β‐keto‐9‐fluorenyliminato ligands with electron‐withdrawing groups (─CF₃), Ni{PhC(O)CHC[N(9‐fluorenyl)]CF₂}₂ (Ni 1 ) and Ni{CF₃C(O)CHC[N(9‐fluorenyl)]Ph}₂ (Ni 2 ), were synthesized by metal coordination reaction and different in situ bonding mechanisms. The C–C bridged bonds of Ni 1 were formed by in situ intramolecular trifluoromethyl and 9‐fluorenyl carbon–carbon cross‐coupling reaction and those of Ni 2 were formed by in situ intramolecular 9‐fluorenyl carbon–carbon radical coupling reaction mechanism. The obtained complexes were characterized using ¹H NMR spectroscopy and elemental analyses. The crystal and molecular structures of Ni 1 and Ni 2 with C–C bridged configuration were determined using X‐ray diffraction. Ni 1 and Ni 2 were used as catalysts for norbornene (NB) polymerization after activation with B(C₆F₅)₃ and the catalytic activities reached 10⁶ g_polymer mol_Ni^?1 h^?1. The copolymerization of NB and styrene catalyzed by the Ni 1 /B(C₆F₅)₃ system showed high activity (10⁵ g_polymer mol_Ni^?1 h^?1) and the catalytic activities decreased with increasing feed content of styrene. All vinyl‐type copolymers exhibited high molecular weight (10⁴ g mol^?1), narrow molecular weight distribution (M_w/M_n = 1.71–2.80), high styrene insertion ratios (11.13–50.81%) and high thermal stability (T_d > 380°C) and could be made into thin films with high transparency in the visible region (400–800 nm).     

Synthesis of dendrimers terminated by DABCO ligands and applications of its palladium nanoparticles for catalyzing Suzuki–Miyaura and Mizoroki–Heck couplings

A new kind of silica‐supported third‐generation dendrimers capped by 1,4‐diaza‐bicyclo[2.2.2]octane (DABCO) group‐stabilized palladium(0) nanoparticles, and their enhanced catalytic activity in Suzuki–Miyaura and Mizoroki–Heck reactions in excellent yield under mild conditions, was reported. The resulting silica‐supported dendrimer‐stabilized palladium(0) nanoparticles with a particle size of 10–20 nm were prepared in situ by treatment with PdCl₂ and hydrazine in ethanol at 60 °C for 24 h. The catalyst as prepared was characterized by FT‐IR, X‐ray diffraction, thermal analysis, elementary analysis (EA), scanning electron microscopy and transmission electron microscopy. Recycling experiments showed that the catalyst could be easily recovered by simple filtration and reused for up to five cycles without losing its activity. Copyright © 2012 John Wiley & Sons, Ltd.     

A heterometal (Pd–Pb) organic framework: synthesis,structure and heterogeneous catalytic application

A heterometallic organic framework {Pb[Pd(bpydc)Cl₂]DMF}_n ( 1 ) (H₂bpydc = 2,2′‐bipyridine‐5,5′‐dicarboxylic acid) was synthesized via a one‐pot solvothermal method and characterized using thermogravimetric analysis, X‐ray photoelectron spectroscopy as well as powder and single‐crystal X‐ray diffraction. The crystal structure of 1 indicates that, in metalloligand Pd(bpydc)Cl₂, every Pd atom adopts a square planar coordination mode with two chloride ions and two nitrogen atoms from bpydc, and the carboxyl groups of Pd(bpydc)Cl₂ connect Pb atoms to form a one‐dimensional chain along the crystallographic a‐axis, which is interlinked via metalloligands to form a two‐dimensional layer structure. This complex is highly active, stable and recyclable as a catalyst for the Suzuki–Miyaura and Heck reactions of a wide range of aryl halides including electron‐rich and electron‐poor aryl iodides/bromides, affording the corresponding products in good to excellent yields. Copyright © 2016 John Wiley & Sons, Ltd.