The Control of the Stereochemistry in the Palladium‐Catalyzed Alternating Styrene/Carbon Monoxide Copolymerization: Effect of the Chirality of the Ligand and of the Ligand‐to‐Palladium Ratio,Preliminary Communication

Diaquapalladium(2+) trifluoromethanesulfonates modified with (4R,4′S)‐ or (4S,4′S)‐2,2′‐bis(4‐benzyl‐4,5‐dihydrooxazole) (C_s‐ and C₂‐ligands) produce isotactic poly(1‐oxo‐2‐phenylpropane‐1,3‐diyl) through copolymerization of styrene with carbon monoxide. However, the same meso‐catalyst in the presence of the free ligand leads to prevailingly syndiotactic growth of the copolymer, whereas the optically active catalyst, when used in the presence of the free enantiomeric ligand, gives an atactic copolymer.     

Kohlenmonoxid/Olefin‐Copolymerisation an einem Organopalladium(II)‐Komplex des Tp*‐Liganden: Langsame CO‐Insertion,langsame Norbornadien‐Insertion,rasche Polyketonbildung

Carbon Monoxide/Olefin Copolymerization catalyzed by an Organopalladium(II) Complex of the Tp* Ligand: Slow Carbon Monoxide Insertion, Slow Norbornadiene Insertion, Rapid Polyketone Formation The Pd complex [PdTp*(p‐tol)(PPh₃)] ( 1 ) of the tridentate ligand Tp* = [HB(3,5‐Me₂pz)₃]^– shows catalytic activity in the copolymerization of carbon monoxide and norbornadiene. 1 inserts carbon monoxide at atmospheric pressure to give the aroyl complex [PdTp*{C(O)p‐tol}(PPh₃)] ( 2 ) within one day. 2 inserts norbornadiene even more slowly to yield the corresponding complex [PdTp*{C₇H₈C(O)p‐tol}] ( 3 ). When both carbon monoxide and olefin are present, polyketone is formed within a few hours. The addition of excess PPh₃ slows down the formation of 2 , but blocks completely the formation of 3 and the formation of polyketone. A reaction mechanism is proposed that can explain these results.     

Linker‐Free,Silica‐Bound Olefin‐Metathesis Catalysts: Applications in Heterogeneous Catalysis

A set of heterogenized olefin‐metathesis catalysts, which consisted of Ru complexes with the H₂ITap ligand (1,3‐bis(2′,6′‐dimethyl‐4′dimethyl aminophenyl)‐4,5‐dihydroimidazol‐2‐ylidene) that had been adsorbed onto a silica support, has been prepared. These complexes showed strong binding to the solid support without the need for tethering groups on the complex or functionalized silica. The catalysts were tested in the ring‐opening–ring‐closing‐metathesis (RO‐RCM) of cyclooctene (COE) and the self‐metathesis of methyl oleate under continuous‐flow conditions. The best complexes showed a TON>4000, which surpasses the previously reported materials that were either based on the Grubbs–Hoveyda II complex on silica or on the classical heterogeneous Re₂O₇/B₂O₃ catalyst.     

Dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylate and bis(dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylato‐κ2N,N′)copper(I) tetrafluoroborate

The single‐crystal X‐ray structures of dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylate, C₁₄H₁₂N₂O₄, and the copper(I) coordination complex bis(dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylato‐κ²N,N′)copper(I) tetrafluoroborate, [Cu(C₁₄H₁₂N₂O₄)₂]BF₄, are reported. The uncoordinated ligand crystallizes across an inversion centre and adopts the anticipated anti pyridyl arrangement with coplanar pyridyl rings. In contrast, upon coordination of copper(I), the ligand adopts an arrangement of pyridyl donors facilitating chelating metal coordination and an increased inter‐pyridyl twisting within each ligand. The distortion of each ligand contrasts with comparable copper(I) complexes of unfunctionalized 2,2′‐bipyridine.     

Polymer Complexes: supramolecular assemblies and structures of poly[N‐(2′‐pyridyl)propenamide] complexes

A number of new polymer complexes of palladium(II), platinum(II) and copper(II) containing homopolymer (N‐(2′‐pyridyl)propenamide; APH) and various anions (Cl^?, Br^?, I^? or NO₃^?) have been synthesized and characterized by elemental analyses, magnetic susceptibility, electron paramagnetic resonance, IR and reflectance spectral measurements. The homopolymer shows three types of coordination behavior. In the mononuclear polymer complexes 1–6 and 9 it acts as a neutral bidentate ligand chelated through the pyridine‐nitrogen and amide‐oxygen atoms, whereas in the square‐planar [Pd(APH)₂X₂] (X = Cl, Br) unidentate APH is coordinated through the pyridine‐nitrogen atom alone. Under alkaline conditions APH is deprotonated in the presence of palladium(II) to form [Pd(AP)₂] ( 10 ), AP being an anionic bidentate ligand and chelating through the pyridine‐nitrogen and amide‐oxygen atoms. The poly‐chelates are of 1:1 and 1:3 (metal:homopolymer) stoichiometry and exhibit six‐coordination. The polymer complexes of stoichiometric [(APH)₂CuX₂] contain square planar (APH)₂ Cu²⁺ units and the anions X^? are in the axial positions, giving distorted octahedral configurations. From the electron paramagnetic resonance and spectral data, the orbital reduction factors were calculated. Copyright © 2004 John Wiley & Sons, Ltd.     

(2,2′‐Bi­pyridine‐κ2N,N′)(2,3‐naph­tha­lene­diolato‐κ2O,O′)­palladium(II) and (2,2′‐bi­quinoline‐κ2N,N′)(2,3‐naph­thal­ene­diolato‐κ2O,O′)­palladium(II)

In the title compounds, [Pd(C₁₀H₆O₂)(C₁₀H₈N₂)], (I), and [Pd(C₁₀H₆O₂)(C₁₈H₁₂N₂)], (II), each Pd^II atom has a similar distorted cis‐planar four‐coordination geometry involving two O atoms of the 2,3‐­naphthalenediolate dianion and two N atoms of the 2,2′‐bi­pyridine or 2,2′‐bi­quinoline ligand. The overall structure of (I) is essentially planar, but that of (II) is not, as a result of intramolecular overcrowding leading to bowing of the bi­quinoline ligand.     

Synthesis,Structural Characterisation and Stereochemical Investigation of Chiral Sulfur‐Functionalised N‐Heterocyclic Carbene Complexes of Palladium and Platinum

Palladium and platinum complexes containing a sulfur‐functionalised N‐heterocyclic carbene (S‐NHC) chelate ligand have been synthesised. The absolute conformations of these novel organometallic S‐NHC chelates were determined by X‐ray structural analyses and solution‐phase 2D ¹H–¹H ROESY NMR spectroscopy. The structural studies revealed that the phenyl substituents on the stereogenic carbon atoms invariably take up the axial positions on the Pd‐C‐S coordination plane to afford a skewed five‐membered ring structure. All of the chiral complexes are structurally rigid and stereochemically locked in a chiral ring conformation that is either (R_s,S,R)‐λ or (S_s,R,R)‐δ in both the solid state and solution.     

Metal Complexes of a Boron‐Dipyrromethene (BODIPY)‐Tagged N‐Heterocyclic Carbene (NHC) as Luminescent Carbon Monoxide Chemodosimeters

Several metal complexes with a boron dipyrromethene (BODIPY)‐functionalized N‐heterocyclic carbene (NHC) ligand 4 were synthesized. The fluorescence in [( 4 )(SIMes)RuCl₂(ind)] complex is quenched (Φ=0.003), it is weak in [( 4 )PdI₂(Clpy)] (Φ=0.033), and strong in [( 4 )AuI] (Φ=0.70). The BODIPY‐tagged complexes can experience pronounced changes in the brightness of the fluorophore upon ligand‐exchange and ligand‐dissociation reactions. Complexes [( 4 )MX(1,5‐cyclooctadiene)] (M=Rh, Ir; X=Cl, I; Φ=0.008–0.016) are converted into strongly fluorescent complexes [( 4 )MX(CO)₂] (Φ=0.53–0.70) upon reaction with carbon monoxide. The unquenching of the Rh and Ir complexes appears to be a consequence of the decreased electron density at Rh or Ir in the carbonyl complexes. In contrast, the substitution of an iodo ligand in [( 4 )AuI] by an electron‐rich thiolate decreases the brightness of the BODIPY fluorophore, rendering the BODIPY as a highly sensitive probe for changes in the coordination sphere of the transition metal.     

Synthesis and Structures of the Ligands 1‐Methylimidazol‐2‐yl(pyridin‐2‐yl)methanone {(py)(mim)CO} and 1‐Benzylimidazol‐2‐yl(1‐phenylaldimine) (PhN=CHbim) as their Tetracarbonylmolybdenum(0) Complexes [Mo(CO)4(L2‐N,N′)]

The complexes [Mo(CO)₄(L₂‐N,N′)] [L₂ = 1‐methylimidazol‐2‐yl(pyridin‐2‐yl)methanone and 1‐benzylimidazol‐2‐yl(1‐phenylaldimine)] have been synthesized from hexacarbonylmolybdenum(0) in order to define the coordination characteristics of the bidentate nitrogen‐donor ligands; the complexes exhibit distorted octahedral coordination for molybdenum(0) and cis‐bidentate ligand configurations.     

Syntheses and Characterizations of Two Palladium(II) Complexes of 5‐Mercapto‐1‐methyltetrazole

Reaction of PdCl₂(CH₃CN)₂ with the sodium salt of 5‐mercapto‐1‐methyltetrazole (MetzSNa) in methanol solution affords an interesting dinuclear palladium complex [Pd₂(MetzS)₄ ] ( 1 ). However, treatment of PdCl₂(CH₃CN)₂ with neutral MetzSH ligand in methanol solution produces a mononuclear palladium complex [Pd(MetzSH)₄]Cl₂ ( 2 ). Both complexes were characterized by IR, ¹HNMR, UV‐Vis spectroscopy as well as X‐ray crystallography. Single‐crystal X‐ray diffraction analyses of two complexes lead to the elucidation of the structures and show that 1 possesses an asymmetric structure: one Pd atom is tetracoordinated by three sulfur atoms and one nitrogen atom to form PdS₃N coordination sphere, the other Pd atom is tetracoordinated by three nitrogen atoms and one sulfur atom to form PdSN₃ coordination sphere. The molecules of 1 are associated to 1‐D infinite linear chain by weak intermolecular Pd···S contacts in the crystal lattice. In 2 , the Pd atom lies on an inversion center and has a square‐planar coordination involving the S atoms from four MetzSH ligands. The two chloride ions are not involved in coordination, but are engaged in hydrogen bonding.     

Synthese,Strukturen und X‐/Q‐Band‐EPR‐Untersuchungen von N,N‐Diethyl‐N′‐3,5‐di(trifluormethyl)benzoylthioureato‐Komplexen des CuII,NiII und PdII sowie EPR‐spektroskopische Charakterisierung eines CuII‐CuII‐Dimers

The synthesis and the structures of (i) the ligand N,N‐Diethyl‐N′‐3,5‐di(trifluoromethyl)benzoylthiourea HEt₂dtfmbtu and (ii) the Ni^II and Pd^II complexes of HEt₂dtfmbtu are reported. The ligand coordinates bidendate forming bis chelates. The Ni^II and the Pd^II complexes are isostructural. The also prepared Cu^II complex could not be characterized by X‐ray analysis. However, the preparation of diamagnetically diluted powders Cu/Ni(Et₂dtfmbtu)₂ and Cu/Pd(Et₂dtfmbtu)₂ suitable for EPR studies was successful. The EPR spectra of the Cu/Ni and Cu/Pd systems show noticeable differences for the symmetry of the CuS₂O₂ unit in both complexes: the Cu/Pd system is characterized by axially‐symmetric g< and A ^cu tensors; for the Cu/Ni system g and A ^Cu have rhombic symmetry. EPR studies on frozen solutions of the Cu^II complex show the presence of a Cu^II‐Cu^II dimer which is the first observed for Cu^II acylthioureato complexes up to now. The parameters of the fine structure tensor were used for the estimation of the Cu^II‐Cu^II distance.     

Five Coordinated Zinc(II) and Tris‐Chelate Cadmium(II) Complexes with 2,2′‐Diamino‐5,5′‐dimethyl‐4,4′‐bithiazole – Syntheses,Spectroscopic Characterization,and Crystal Structure

The new synthesized ligand (DADMBTZ = 2,2′‐diamino‐5,5′‐dimethyl‐4,4′‐bithiazole), which is mentioned in this text, is used for preparing the two new complexes [Zn(DADMBTZ)₃](ClO₄)₂. 0.8MeOH.0.2H₂O ( 1 ) and [Cd(DADMBTZ)₃](ClO₄)₂ ( 2 ). The characterization was done by IR, ¹H, ¹³C NMR spectroscopy, elemental analysis and single crystal X‐ray determination. In reaction with DADMBTZ, zinc(II) and cadmium(II) show different characterization. In 2 , to form a tris‐chelate complex with nearly C₃ symmetry for coordination polyhedron, DADMBTZ acts as a bidentate ligand. In 1 , this difference maybe relevant to small radii of Zn²⁺ which make one of the DADMBTZ ligands act as a monodentate ligand to form the five coordinated Zn²⁺ complex. In both 1 and 2 complexes the anions are symmetrically different. 1 and 2 complexes form 2‐D and 3‐D networks via N‐H···O and N‐H···N hydrogen bonds, respectively.     

Supramolecular Stuctures from Mononuclear,Binuclear and 2D Net of Copper(II) Complexes with 6‐Hydroxypicolinic Acid

First examples of transition metal complexes with HpicOH [Cu(picOH)₂(H₂O)₂] ( 1 ), [Cu(picO)(2,2′‐bpy)]·2H₂O ( 2 ), [Cu(picO)(4,4′‐bpy)_0.5(H₂O)]_n ( 3 ), and [Cu(picO)(bpe)_0.5(H₂O)]_n ( 4 ) (HpicOH = 6‐hydroxy‐picolinic acid; 2,2′‐bpy = 2,2′‐bipyridine; 4,4′‐bpy = 4,4′‐bipyridine; bpe = 1,2‐bis(4‐pyridyl)ethane) have been synthesized and characterized by single‐crystal X‐ray diffraction. The results show that HpicOH ligand can be in the enol or ketonic form, and adopts different coordination modes under different pH value of the reaction mixture. In complex 1 , HpicOH ligand is in the enol form and adopts a bidentate mode. While in complexes 2 – 4 , as the pH rises, HpicOH ligand becomes in the ketonic form and adopts a tridentate mode. The coordination modes in complexes 1 – 4 have not been reported before. Because of the introduction of the terminal ligands 2,2′‐bpy, complex 2 is of binuclear species; whereas in complexes 3 and 4 , picO ligands together with bridging ligands 4,4′‐bpy and bpe connect Cu^II ions to form 2D nets with (12³)₂(12)₃ topology.     

Three‐Component Self‐Assembly of a Series of Triply Interlocked Pd12 Coordination Prisms and Their Non‐Interlocked Pd6 Analogues

Template‐assisted formation of multicomponent Pd₆ coordination prisms and formation of their self‐templated triply interlocked Pd₁₂ analogues in the absence of an external template have been established in a single step through Pd? N/Pd? O coordination. Treatment of cis‐[Pd(en)(NO₃)₂] with K₃tma and linear pillar 4,4′‐bpy (en=ethylenediamine, H₃tma=benzene‐1,3,5‐tricarboxylic acid, 4,4′‐bpy=4,4′‐bipyridine) gave intercalated coordination cage [{Pd(en)}₆(bpy)₃(tma)₂]₂[NO₃]₁₂ ( 1 ) exclusively, whereas the same reaction in the presence of H₃tma as an aromatic guest gave a H₃tma‐encapsulating non‐interlocked discrete Pd₆ molecular prism [{Pd(en)}₆(bpy)₃(tma)₂(H₃tma)₂][NO₃]₆ ( 2 ). Though the same reaction using cis‐[Pd(NO₃)₂(pn)] (pn=propane‐1,2‐diamine) instead of cis‐[Pd(en)(NO₃)₂] gave triply interlocked coordination cage [{Pd(pn)}₆(bpy)₃(tma)₂]₂[NO₃]₁₂ ( 3 ) along with non‐interlocked Pd₆ analogue [{Pd(pn)}₆(bpy)₃(tma)₂](NO₃)₆ ( 3′ ), and the presence of H₃tma as a guest gave H₃tma‐encapsulating molecular prism [{Pd(pn)}₆(bpy)₃(tma)₂(H₃tma)₂][NO₃]₆ ( 4 ) exclusively. In solution, the amount of 3′ decreases as the temperature is decreased, and in the solid state 3 is the sole product. Notably, an analogous reaction using the relatively short pillar pz (pz=pyrazine) instead of 4,4′‐bpy gave triply interlocked coordination cage [{Pd(pn)}₆(pz)₃(tma)₂]₂[NO₃]₁₂ ( 5 ) as the single product. Interestingly, the same reaction using slightly more bulky cis‐[Pd(NO₃)₂(tmen)] (tmen=N,N,N′,N′‐tetramethylethylene diamine) instead of cis‐[Pd(NO₃)₂(pn)] gave non‐interlocked [{Pd(tmen)}₆(pz)₃(tma)₂][NO₃]₆ ( 6 ) exclusively. Complexes 1 , 3 , and 5 represent the first examples of template‐free triply interlocked molecular prisms obtained through multicomponent self‐assembly. Formation of the complexes was supported by IR and multinuclear NMR (¹H and ¹³C) spectroscopy. Formation of guest‐encapsulating complexes ( 2 and 4 ) was confirmed by 2D DOSY and ROESY NMR spectroscopic analyses, whereas for complexes 1 , 3 , 5 , and 6 single‐crystal X‐ray diffraction techniques unambiguously confirmed their formation. The gross geometries of H₃tma‐encapsulating complexes 2 and 4 were obtained by universal force field (UFF) simulations.     

Three Transition Metal(II) Coordination Polymers Constructed by a Semi‐rigid Bis‐pyridyl‐bis‐amide and Dicarboxylates Mixed Ligands: Assembly,Structures and Properties

Three coordination polymers, namely [Co(BDC)( L )] · H₂O ( 1 ), [Co(NPH)( L )] · H₂O ( 2 ), and [Ni(NPH)( L )(H₂O)₃] · H₂O ( 3 ) [H₂BDC = 1, 3‐benzenedicarboxylic acid, H₂NPH = 3‐nitrophthalic acid, L = N,N′‐bis(3‐pyridyl)‐terephthalamide] were hydrothermally synthesized by self‐assembly of cobalt/nickel chloride with a semi‐rigid bis‐pyridyl‐bis‐amide ligand and two aromatic dicarboxylic acids. Single crystal X‐ray diffraction analyses revealed that complexes 1 and 2 are two‐dimensional (2D) coordination polymers containing a one‐dimensional (1D) ribbon‐like Co‐dicarboxylate chain and a 1D zigzag Co‐ L chain. Although the coordination numbers of Co^II ions and the coordination modes of two dicarboxylates are different in complexes 1 and 2 , they have a similar 3, 5‐connected {4².6⁷.8}{4².6} topology. In complex 3 , the adjacent Ni^II ions are linked by L ligands to form a 1D polymeric chain, whereas the 1D chains does not extend into a higher‐dimensional structure due to the ligand NPH with monodentate coordination mode. The adjacent layers of complexes 1 and 2 and the adjacent chains of 3 are further linked by hydrogen bonding interactions to form 3D supramolecular networks. Moreover, the thermal stabilities, fluorescent properties, and photocatalytic activities of complexes 1 – 3 were studied.     

Iridium Complexes of 2,2′‐Bidipyrrins

The reaction of [{Ir(cod)(μ‐Cl)}₂] and K₂CO₃ or of [{Ir(cod)(μ‐OMe)}₂] alone with the non‐natural tetrapyrrole 2,2′‐bidipyrrin (H₂BDP) yields, depending on the stoichiometry, the mononuclear complex [Ir(cod)(HBDP)] or the homodinuclear complex [{Ir(cod)}₂(BDP)]. Both complexes react readily with carbon monoxide to yield the species [Ir(CO)₂(HBDP)] and [{Ir(CO)₂}₂(BDP)], respectively. The results from NMR spectroscopy and X‐ray diffraction reveal different conformations for the tetrapyrrolic ligand in both complexes. The reaction of [{Ir(coe)₂(μ‐Cl)}₂] with H₂BDP proceeds differently and yields the macrocyclic [4e^?,2H⁺]‐oxidized product [IrCl₂(9‐Meic)] (9‐Meic = monoanion of 9‐methyl‐9,10‐isocorrole), which can be addressed as an iridium analog of cobalamin.     

A Remarkable cis‐ and trans‐Spanning Dibenzylidene Acetone Diphosphine Chelating Ligand (dbaphos)

A multidentate and flexible diolefin–diphosphine ligand, based on the dibenzylidene acetone core, namely dbaphos ( 1 ), is reported herein. The ligand adopts an array of different geometries at Pt, Pd and Rh. At Pt^II the dbaphos ligand forms cis‐ and trans‐diphosphine complexes and can be defined as a wide‐angle spanning ligand. ¹H NMR spectroscopic analysis shows that the β‐hydrogen of one olefin moiety interacts with the Pt^II centre (an anagostic interaction), which is supported by DFT calculations. At Pd⁰ and Rh^I, the dbaphos ligand exhibits both olefin and phosphine interactions with the metal centres. The Pd⁰ complex of dbaphos is dinuclear, with bridging diphosphines. The complex exhibits the coordination of one olefin moiety, which is in dynamic exchange (intramolecular) with the other “free” olefin. The Pd⁰ complex of dbaphos reacts with iodobenzene to afford trans‐[Pd^II(dbaphos)I(Ph)]. In the case of Rh^I, dbaphos coordinates to form a structure in which the phosphine and olefin moieties occupy both axial and equatorial sites, which stands in contrast to a related bidentate olefin, phosphine ligand (“Lei” ligand), in which the olefins occupy the equatorial sites and phosphines the axial sites, exclusively.     

Effect of Metal Ions on the Structures of Coordination Polymers Based on Biphenyl‐2,2′,4,4′‐Tetracarboxylate

Two new coordination polymers, {[Cd₂(btc)(2,2′‐bpy)₂] · H₂O}_n ( 1 ) and [Zn₂(btc)(2,2′‐bpy)(H₂O)]_n ( 2 ) (H₄btc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine), were synthesized hydrothermally under similar conditions and characterized by elemental analysis, IR spectra, TGA, and single‐crystal X‐ray diffraction analysis. In complexes 1 and 2 , the (btc)^4– ligand acts as connectors to link metal ions to give a 2D bilayer network of 1 and a 3D metal‐organic framework of 2 , respectively. The differences in the structures are induced by diverging coordination modes of the (btc)^4– ligand, which can be attributed to the difference metal ions in sizes. The results indicate that metal ions have significant effects on the formation and structures of the final complexes. Additionally, the fluorescent properties of the two complexes were also studied in the solid state at room temperature.     

Palladium‐MOP Chemistry: Pseudo‐cis‐Allyl MOP Complexes and Flexible Olefin Bonding. Preliminary Communication

We show that both palladium(0) and palladium(II) metal centers are capable of coordinating two monodentate MOP (=(R)‐2‐(diarylphosphino)‐1,1′‐binaphthalene) ligands in a pseudo‐cis orientation, despite published statements to the contrary. In addition to [Pd(η³‐C₃H₅)(MeO? MOP)₂]BF₄ (MeO? MOP=(R)‐2‐(diphenylphosphino)‐2′‐methoxy‐1,1′‐binaphthalene), the first examples of chiral bis κC¹‐prop‐2‐enyl (η¹‐CH₂CH?CH₂) complexes [cis‐Pd(κC¹‐C₃H₅)₂(MeO? MOP or MOP)₂], are shown to be relatively stable. Further, coordinated MOP and MeO? MOP both show stronger propensity towards novel intramolecular π‐olefin complexation than the CN? MOP analogue. The solid‐state structure of [Pd(fumaronitrile)(MOP)₂] is reported.     

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