Samarium(II) Diiodide Induced Polarity Inversion of π-Allyl Palladium Complexes: The Formation of Allylic Selenides

Allylic acetates were reduced with Pd(0)-SmI2 in the presence of ArSeBr to form corresponding allylic selenides in good yields.

Ionic palladium complex as an efficient and recyclable catalyst for the carbonylative Sonogashira reaction

The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-3-methylimidazolium]dichloropalladium（Ⅱ） trifluoromethanesulfonate（2A） ligated by thiazolylimidazolium-based phosphine（L2） after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.

Chitosan-immobilized Palladium Complex: a Green and Highly Active Heterogeneous Catalyst for Heck Reaction

A green heterogeneous catalyst for Heck reaction-chitosan-immobilized palladium complex was prepared. The catalyst exhibits high activity and stereoselectivity under the moderate reaction conditions. The catalyst can be separated easily from the reaction mixture and reused after washing. Under the suitable reaction conditions, the cross-coupling of iodobenzene (ArI) with acrylic acid (AA) or acrylate can be achieved 93.3% or 99% yield of trans-cinnamic acid or trans-cinnamic ester.

Synthesis, Structure and Norbornene Polymerization Catalyzed by Palladium Complex Bearing the 1,3-Diphenyl-2-((quinolin-8-ylamino)-methylene)-propane-1,3-dione Ligand

The title complex 1,3-diphenyl-2-（（quinolin-8-ylamino）methylene）propane-l,3- dione-palladium was synthesized by the reaction of 1,3-diphenyl-2-（（quinolin-8-ylamino）-methylene）propane-1,3-dione with PdCl2, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the orthorhombic system, space group P21212 with a = 21.838（4）, b = 8.3952（17）, c = 11.497（2） A, V= 2107.9（7） A3, C25H17C1N2O2Pd, Mr = 519.26, Z= 4, Dc= 1.636 g/cm3, H = 1.032 mm-1, F （000） = 1040, the final R = 0.0307 and wR = 0.0778. This compound was investigated for the catalytic behavior towards norbornene （NB） vinyl addition polymerization. And the complex exhibits excellent catalytic activities up to 2.18×10^8g of PNB （tool of Pd）-1 h-1 with high monomer conversion using methylaluminoxane （MAO） as the cocatalyst.

Suzuki reaction of bromoallenes with arylboronic acids using an air-stable palladium complex Pd(Ph_2PCH_2CO_2)_2 as a precatalyst

Suzuki reaction of bromoallenes with arylboronic acids was successfully performed by using an air-stable hemilabile P-O coordinated cyclopalladated complex Pd(Ph_2PCH_2CO_2)_2 as a precatalyst,and the corresponding coupling products were obtained in satisfactory to excellent yields.All products are unknown compounds which were characterized by ~1H NMR,^(13)C NMR,IR,and HRMS.

Synthesis of a New Type of Amphilic and Water - soluble Tertiary Phosphine Ligands Substituted by an Ethoxylated Phosphonic Acid Chain and Their Palladium Complexes

The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N- (CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (II) complexes of the ligands 3a~c with 2:1 or 4:1 -PPh2 to Pd2+ molar ratio were also prepared and characterized .

HYDROGENATION OF PHENOL AND CRESOLS CATALYZED BY CHITOSAN SUPPORTED PALLADIUM COMPLEX AT MILD CONDITIONS

A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% selectivity at 70 degrees C and 1.01325 x 10(5) Pa mild conditions. N/Pd molar ratio in the complex, temperature and solvents have much influence on the reaction. The reactivity order of reactants was found to be: phenol >m->p->o- The catalyst is stable during the reaction and could be repeatedly used for several times without much decrease in its catalytic activity.

Canon-π Interactions. Synthesis and Crystal Structure of Palladium Complex:[K(DB18C6)]_2[Pd(SCN)_4]

A novel Pd(Ⅱ)-dibenzo-18-crown-6(DB18C6) complex [K(DB18C6)]_2, [Pd(SCN)_4] has been isolated and characterized by X-ray diffraction analysis. In the solid state, it displays a quasi- one-dimensional infinite chain of two [K(DB18C6)]+ complex canons and a [Pd(sCN)_4]^(2-) anion bridged by K+-π interactions between adjacent [K(DB18C6)] + units.

A New Humidity-Sensitive Material Based on PPBT Prepared with Palladium Complex Catalyst

Soluble Poly(propargyl benzoate) (PPBT) with pi -conjugated structure was synthesized using a novel bis(triphenylphosphine)-bisacetylide palladium complex catalyst [Pd(PPh3)(2)(C equivalent to CCH2OOCPh)(2)] (PPB). An interdigital gold electrode was covered by screen printing films of doped PPBT (DPPBT) to prepare a resistance-type humidity sensor, which exhibits electrical response towards relative humidity (RH%) variations in the range 11%-96%. PPBT shows promise as a new humidity-sensitive material.

Synthesis and Characterization of a Palladium Complex Supported by Bidentate Ligand and Catalysis of the Vinyl Polymerization of Norbornene

The title complex N,O-bis{[2-[（2,4-dimethylphenyl）imino]-5-methoxyl]-phenol}-palladium（Ⅱ）（CC_（32）H_（32）N_2O_4Pd） has been synthesized by the reaction of 2-[（2,4-dimethylphenyl）imino]-5-methoxyl-phenol with Pd（CH_3COO）_2,and characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction analysis.The crystal belongs to the monoclinic system,space group P2_1/c with a = 12.058（2）,b = 8.3624（17）,c = 14.735（3） ？,β = 107.66（3）°,V = 1415.7（5）？~3,C_（32）H_（32）N_2O_4Pd,Mr = 615,Z = 2,D_c = 1.443 Mg/m^3,μ = 0.695 mm^（-1）,F（000） = 632,T = 293（2） K,the final R = 0.0514 and w R = 0.1356（I 〉 2s（I））.Under the co-catalysis of methylaluminoxane（MAO）,the palladium compound exhibited favorable catalytic activity for the polymerization of norbornene（NB）.

SOLID-LIQUID PHASE TRANSFER AND COBALT OR PALLADIUM COMPLEX CATALYZED SYNTHESIS OF ANHYDRIDES FROM ACYL CHLORIDES

Acyl chloride can efficiently be converted into anhydride under solid liquid phase transfer catalysis by using bis(triphenylphosphine)cobalt dichloride or bis(triphenylphospine)palladium dichloride as the catalyst.

SYNTHESIS AND CHARACTERIZATION OF ZEROVALENT PALLADIUM COMPLEXES

A series of nine Pd(0)complexes(L)Pd(L')[L=bis(diphenylphosphino) methane(dppm),1,2-bis(diphenylphosphino)ethane(dppe),and 1,1'-bis(diphenyl- phosphino)ferrocene(dppf),respectively;L=dibenzylideneacetone(dba),2,3,5, 6-tetrachloro-1.4-benzoquinone(q)and 2,3-dichloro-1,4-naphthoquinone(nq)] were synthesized and characterized by means of elemental analyses,IR,UV, 1~H-NMR and^(31)P-NMR spectra.The redox wave peak potentials of the ferrocenyl group of complexes with dppf were measured by using CV method.Results showed that all the diphosphorus ligands behaved as chelating bidentate ligand and dba,q,nq were coordinated to the Pd(0)atom through their C=C moieties,not their carbonyl ones.Analytical data also showed that there were interactions between the two different ligands in each complex.

Chiral palladium complexes based on derivatives of benzylamine and 2α-hydroxypinan-3-one

Synthesized and characterized new chiral palladium complexes, some of which contain asymmetric donor nitrogen atom. Nitrogen-containing derivatives (+) - and (-)-2α-hydroxypinan-3-one- (1R,2R,5R)-3-(benzylimino)-2,6,6-trimethylbicy- clo[3.1.1]heptane-2-ol (HL1), (1S,2S,3S,5S)-3- (benzylamino)-2,6, 6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL2), (1R,2R,5R)-3-((S)-α-methyl- benzylimino)-2,6,6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL3), (1R,2R,3R,5R)-3-((S)-α-methyl- benzylamino)-2,6,6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL4) -were studied as optically active ligands.

Catalytic Hydrogenation over Palladium Complex of Molecular Complex of Poly(4-vinylpyridine) with Acetic Acid

The palladium complex of the molecular complex of poly(4 vinylpyridine) with acetic acid(PVP/ HAc Pd) was prepared. Its catalytic activity for the hydrogenation of nitrobenzene was found much higher than that of the corresponding palladium complex of poly(4 vinylpyridine). In the presence of a strong inorganic alkali, especially potassium hydroxide, the catalytic activity is greatly improved. The suitable hydrogenation condition for PVP/HAc Pd is to use 0 1 mol/L ethanol solution of potassium hydroxide as the hydrogenation medium and the hydrogenation is carried out at 45 ℃.

Palladium Complexes with N,O-Bidentate Ligands Based on N-Oxide Units from Cyclic Secondary Amines:Synthesis and Catalytic Application in Mizoroki-Heck Reaction

Palladium-catalyzed Mizoroki-Heck reaction is a powerful and efficient method for construction of Csp2–Csp2 bonds.Herein,four palladium complexes(I—IV)with N,O-bidentate ligands(L1—L4)based on N-oxide units from cyclic secondary amines were easily synthesized and successfully applied in Mizoroki-Heck reaction of aryl bromides with electron-deficient olefins.X-ray diffraction analyses indicated the palladium(II)atom of II took the distorted square planar geometry and was four-coordinated by nitrogen and oxygen atoms from two ligands(L2).Two free chloride ions were presented as counter anions in complex II.But the palladium(II)center of IV was coordinated by nitrogen and oxygen atoms from one ligand(L4)as well as two chlorine atoms,which exhibited the nearly square-planar geometry.The study on catalytic properties of palladium complexes revealed that complex II exhibited high activity superior to the other complexes.The coupling reactions of a series of aryl bromides and olefin derivatives proceeded in the presence of 2—5 mol%palladium complex II,giving the desired products in good to excellent yields.The advantages of this method such as good compatibility of functional groups,high yields,and short reaction times made it more attractive for constructing Csp2–Csp2 bonds in the synthesis of functional molecules and materials.

Synthesis of axially chiral oxazoline–carbene coordinated palladium complexes with a N-phenyl framework

A family of tropos ligands bearing a N-heterocyclic carbene and a chiral oxazoline coordination group with a N-phenyl framework were easily prepared,and their coordination behavior with Pd（Ⅱ）acetate was performed,affording a series of axially chiral palladium complexes in good yields.

The Novel Benzo-15-Crown-5 with Palladium(II) Complex: [Na(B15CS)]_2,[Pd(SCN)_4]

A novel Pd(II) Benzo-15-crown-5 complex [Na(B15CS)]_2[Pd(SCN)_4] has been isolated and characterized by IR and X-ray diffraction analysis. The crystal structure belongs to monoclinic, space group P2_1,/n with cell dimensions, a = l.0164(6), b = l.3743(3), c = l.4987(7) nm, β = 95.248(6) °, V = 2.0847 'nm_3, Z = 2, F(000) = 944, R = 0.053, Rw = 0.072. The compound consists of two [Na(B15CS)]+ complex canons and a [Pd(SCN)4_]^(2-) complex anion. Each sodium ion is coordinated by five crown ether oxygen atoms and one N atom from the SCN group of [Pd(SCN)_4]^(2-) to form stable neutral complex.

Synthesis, Structure and Norbornene Polymerization Catalyzed by o-Benzene Diimine Di-nuclear Palladium(Ⅱ) Complex

The title complex, C20H17N4Pd2Cl3·0.5CH3OH, crystallizes in the triclinic system, space group Pī with α = 9.927（6）, b = 11.079（6）, c = 11.233（6） ？, a = 73.970（12）, β = 85.738（16）, γ = 83.300（12）o, V = 1178.1（11） ？3, Mr = 648.55, Z = 2, Dc = 1.520 g/cm3, μ = 1.884 mm-1, F（000） = 634, the final R = 0.0460 and wR = 0.1280. This title compound was investigated for the catalytic behavior towards norbornene （NB） vinyl addition polymerization. And the complex exhibits good catalytic activity to catalyze norbornene polymerization using MAO as a cocatalyst.

Synthesis and Crystal Structure of Palladium(Ⅱ) Complex with 2,2’-Bipyridine-3,3’-dicarboxylic Acid

The title complex Pd（H2BDA）Cl2·2DMSO （C16H14Cl2N2O6PdS2, H2BDA = 2,2＇- bipyridine-3,3＇-dicarboxylic acid） has been synthesized and characterized by IR spectra, elemental analysis and ^1H NMR spectra. Its structure was determined by single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic system, space group P2（1/c） with a = 1.3604（6）, b = 1.2606（6）, c = 1.3521 （6） nm, β = 103.677（7）°, V = 2.2530（17） nm^3, Mr = 571.75, Z = 4, Dc = 1.686 g/cm^3,μ = 1.280 mm^-1, F（000） = 1136, R= 0.0405 and wR= 0.0908. The complex presents a planar quadrangle arrangement and is assembled via hydrogen bonds.

Synthesis,Structure and Norbornene Polymerization Activity of a Novel Palladium(Ⅱ) Complex with N,N-bis(2-benzoyl-3-oxobutane)-trans-1,2-diaminocyclohexane Ligand

The title complex N,N＇-bis（2-benzoyl-3-oxobutane）-trans-l,2-diaminocyclo- hexane-palladium （C28H28N2PdO4） has been synthesized by the reaction of N,N＇-bis（2- benzoyl-3-oxobutane）-trans-l,2-diamino-cyclohexane with PdCI2, and characterized by ele- mental analysis, IR spectrum, WAXD and TG. The spatial structures of the complex have been confirmed by single-crystal X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group C2/c with a = 29.763（6）, b = 10.320（2）, c = 18.921（4） A, fl = 102.75（3）°, V = 5668（2） A3, C28H28N2PdO4·CH3OH, Mr = 594.97, Z = 8, Dc = 1.394 g/cm3, μ（MoKa） = 0.694 mm-1, F（000） = 2448, T= 293（2） K, R = 0.0572 and wR = 0.1347 （I〉 2σ（I））. The compound was investigated for the catalytic behavior towards norbornene （NB） vinyl addition polymerization. And the palladium complex showed excellent catalytic activity up to 9.97x 106g of PNB （mol of Pd）-1 h-1 with high monomer conversion using methylaluminoxane （MAO） as a cocatalyst.