基于含有硫醚基团的吡啶烷基酰胺配体的铜配合物的合成和结构表征（英文）

合成和表征了含有硫醚基团的吡啶烷基酰胺配体2-(甲硫基)-N-[2-(2-吡啶)甲基]乙酰胺(HL1)和2-(甲硫基)-N-[2-(2-吡啶)乙基]乙酰胺(HL2)及其3个铜的配合物,{[Cu(L1)(CH3OH)](OTf)}n(1)(Otf=三氟甲磺酸根),{[Cu(L2)(OTf)]·CH3OH}n(2)和[Cu(HL2)(CH3OH)Cl](3),并通过X-射线单晶衍射分析确定了其晶体结构。配合物1和2均为含有铜的一维配位聚合物,而配合物3为单核铜配合物。分析了配合物中铜离子的配位特点及可能的形成原因。

Two novel Cu(Ⅰ)complexes based on diimide and bisphosphine ligands:synthesis,crystal structure and spectroscopic properties

Two Cu(Ⅰ)complexes[Cu(Bphen)(dppBz)]ClO_(4)·2CH_(3)OH(1)and[Cu_(2)(Bphen)_(2)(dpppda)]BF_(4)(2){Bphen=4,7-diphenyl-1,10-phenanthroline,dppBz=1,2-Bis(diphenylphosphino)benzene,dpppda=N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamin}were synthesized using a one-pot method.X-ray crystallography was used to elucidate their crystal structures and photophysical properties.A series of characterization tests including elemental analysis,NMR,FT-IR,UV-Vis absorption spectroscopy,fluorescence spectroscopy,thermal gravimetric analysis and terahertz time-domain spectroscopy(THz-TDS)were used to further investigate their properties.The results show that complex 1 structure is mononuclear containing two solvent molecules per unit cell,while complex 2 structure is binuclear containing two metal centers per unit cell.According to photophysical properties and density functional theory(DFT)calculations,their luminescence properties can be attributed to metal-to-ligand charge transfer(MLCT).Both complexes have a unique stability,which is confirmed by thermal gravimetric analysis.

Synthesis of ultrafine copper particles by complex-reduction-extraction method

A novel chemical process for producing well-defined copper particles with satisfied anti-oxidation property was described. The resultant particles were characterized by X-ray diffractometry and scanning electron microscopy. The results show that well-dispersed nano-copper particles with 70 nm in diameter are obtained from the water/organic solution containing 0.2 mol/L Cu2+ ion,with ammonia as ligand and ascorbic acid as reductant. In this process,the formation of copper-ligands in aqueous solution causes initial copper ions concentration very low,which is not only good to obtain homogeneous initial reaction solution,but also slower the initially drastic nucleation reaction rate. This makes the process more convenient for delaying the nuclei processes and for controlling the ultimate copper particles size. In addition,oleic acid acts as both a phase-transfer agent and a particle protector coordinating their carboxyl end groups on the new generated copper particles surface,the carbon tails of the oleic acids are pointed outwards from the surface of the synthesized particles. This organic film also seems to play an important role to prevent the new generated copper particles from oxidation.

Synthesis, crystal structure and magnetic properties of novel copper compound Cu(phen)(m-CBA)_2

A novel compound Cu（phen）（m-CBA）2 was synthesized with m-chlorobenzoic acid（m-CBA）, 1,10-phenanthroline（phen） and Cu（OAc）2·H2O. It was characterized by IR, UV, elemental analyses and X-ray crystallography. It crystallizes in the monoclinic crystal system with C2/c space group, a=2.9699（4） nm, b=1.15452（2） nm, c=1.5335（2） nm, β=111.118（2）°, V=4.905 1（1） nm3, Z=8, F（000）=2 328, R1=0.072 8, wR2=0.223 4 [I2σ（I）]. Structure analysis shows that the copper center coordinates with two nitrogen atoms from one 1,10-phenanthroline molecule, two oxygen atoms from two m-chlorobenzoic acid molecules, giving a distorted squared planar coordination geometry. This novel compound shows paramagnetic interactions between copper centers.

Highly active binuclear Cu(Ⅱ) catalyst bearing an unsymmetrical bipyridine-pyrazole-amine ligand for the azide-alkyne cycloaddition reaction

Ligands containing NH groups often show special characteristics.In this paper,a well-defined dinuclear Cu（II） complex bearing an unsymmetrical bipyridine-pyrazole-amine ligand was synthesized by the condensation of N–H to release H2O.Using sodium L-ascorbate as a reductant,the binuclear complex showed excellent activity in 1,3-dipolar cycloaddition reactions between alkynes and azides to obtain 1,4-disubstituted triazoles in 95%–99% isolated yields.

Synthesis and Structure of Copper(Ⅱ) Complex [Cu(C_5H_5N)_2(H_2O)(C_6H_5COO)_2]

At room temperature, the reaction of dibenzoyl peroxide with metallic copper powder in the presence of pyridine affords the copper(Ⅱ) complex [Cu(C 5H 5N) 2(H 2O)\|(C 6H 5COO) 2]. Crystal is monoclinic, M r =483.002, space group Cc with parameters: a=6\^078(4), b=15.879(4), c=23.091(3), β=97.61(2)°, V=2209.1(2) 3, Z=4, D c =1\^464g/cm 3, μ =10.279 cm -1 , F(000)=996, R=0\^031, R w =0.036, 1595 reflections with I≥3σ(I ) were considered to be observed. Each copper(Ⅱ) ion is coordinated by two monodentate benzoate ligands, two pyridines and one water molecule. The complex is also characterized by its IR, XPS and thermal properties.

Synthesis and Structure of anti-Configuration Complex [Cu(tssb)_2]·2[(H_3O)Cl]·4H_2O

The title complex [Cu(tssb)2]2[(H3O)Cl]4H2O (C18H34Cl2CuN2O14S2) (tssb = tau- rine salicylaldehyde Schiff base) has been synthesized by the reaction of taurine salicylaldehyde Schiff base (tssb) and copper acetate in water-ethanol. Its single-crystal structure was determined by X-ray diffraction method. The crystal structure belongs to triclinic, space group P1 with a = 0.7407(1), b = 1.3329(3), c = 1.5736(3) nm, ?= 103.800(4), ?= 95.030(4), ?= 104.416(4)? Mr = 701.06, V = 1.4433(5) nm3, Z = 2, Dc = 1.613 g/cm3, = 1.153 mm-1 and F(000) = 726. The compound is an infinitely expanding three-dimensional network connected with hydrogen bonds. The Cu(Ⅱ) atom is coordinated by two nitrogen and two oxygen atoms to form a distorted planar coordination compound which adopts anti-configuration because two sulfonic acid groups are posi- tioned diagonally on a plane.

Buffer anion effects on water oxidation catalysis: The case of Cu(Ⅲ) complex

Water oxidation is the bottleneck of artificial photosynthesis.Since the first ruthenium-based molecular water oxidation catalyst,the blue dimer,was reported by Meyer’ s group in 1982,catalysts based on transition metals have been widely employed to explore the mechanism of water oxidation.Because the oxidation of water requires harsh oxidative conditions,the stability of transition complexes under the relevant catalytic conditions has always been a challenge.In this work,we report the redox properties of a CuⅢ complex(TAML-CuⅢ] with a redox-active macrocyclic ligand(TAML) and its reactivity toward catalytic water oxidation.TAML-CuⅢ displayed a completely different electrochemical behavior from that of the TAML-CoⅢ complex previously reported by our group.TAML-CuⅢ can only be oxidized by one-electron oxidation of the ligand to form TAML·+-CuⅢand cannot achieve water activation through the ligand-centered proton-coupled electron transfer that takes place in the case of TAML-CoⅢ.The generated TAML·+-CuⅢ intermediate can undergo further oxidation and ligand hydrolysis with the assistance of borate anions,triggering the formation of a heterogeneous B/CuOx nanocatalyst Therefore,the choice of the buffer solution has a significant influence on the electrochemical behavior and stability of molecular water oxidation catalysts.

Synthesis and Crystal Structure of Copper (Ⅱ) Compound with 3,3'-Azobispyridine Ligand [Cu(NO_3)_2(H_2O)_2(3,3'azpy)_2]

The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic parameters: a = 7.4161(2), b = 8.1754(3), c = 10.7545(4) ? a = 92.958(2), b = 109.978(1), g = 93.369(2)? V = 609.96(4) ?, C20H20N10CuO8, Mr = 592.00, Dc = 1.612 g/cm3, m(MoKa) = 0.964 mm-1, F(000) = 303, Z = 1, the final R = 0.0494 and wR = 0.1269 for 1945 observed reflections (I > 2s(I)). X-ray analysis reveals that the Cu atom adopts a distorted octahedral (4 + 2) coordination. The four closer donor atoms include two N atoms of 3,3?azpy and two O atoms of the coordination aqua with the CuN and CuO distances of 2.014(3) and 1.974(3) ? respectively. Two longer out-of-plane CuO bonds (2.450(3) ? from nitrate complete the strongly distorted octahedral coordination of the Cu atom. Hydrogen bonds are formed through H atoms of each coordination aqua with the remaining N atoms of 3,3?azpy and O atoms of nitrate. A two-dimensional network is constructed by hydrogen bonds and p-p interactions.

Synthesis and Crystal Structure of {Cu_2(pdc)_2(4,4'-bipy)(H_2O)·3H_2O}_2

The title compound {Cu2(pdc)2(4,4?-bipy)(H2O)3H2O}2 1 (H2pdc = pyridine-2,6- dicarboxylic acid, also known as dipicolinic acid; 4,4?-bipy = 4,4?-bipyridine) has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pi with a = 7.2278(3), b = 10.6259(4), c = 17.7614(6) ? a = 79.5990(10), = 83.6300(10), ? = 71.8280(10)o, V = 1272.60(8) ?, C48H44Cu4N8O24, Mr = 1371.07, Z = 1, Dc = 1.789 g/cm3, = 1.747 mm-1, F(000) = 696, R = 0.0397 and wR = 0.1137 for 3938 observed reflections (I > 2s(I)). There are two kinds of Cu coordination environments, and each central copper(II) atom is five-coordinated in a distorted square-based pyramidal coordination geo- metry. Four copper(II) atoms are linked by four pdc and two 4,4?-bipy ligands to form an annular rectangle structure. Extensive hydrogen-bonding interactions involving carboxylate O atoms as well as coordinated and free water molecules lead to the formation of a three-dimensional network struc- ture.

Kinetic study on reactive extraction of phenylalanine enantiomers with BINAP-copper complexes

Enantioselective liquid–liquid extraction has attracted considerable attention for its potential use in largescale production. Kinetic data are needed for the reliable scale-up of the process. This paper reports the kinetic study of reactive extraction of phenylalanine(Phe) enantiomers with BINAP–copper complex(BINAP–Cu) as a chiral selector. The theory of extraction accompanied by a chemical reaction was applied.The effects of agitation speed, interfacial area, p H value of aqueous phase, initial concentration of Phe enantiomers and initial concentration of BINAP–Cu on the specific rate of extraction were investigated. The forward rate constants of the reactions in the reactive extraction process are 7.93 × 10-5m5/2·mol-1/2·s-1for D-Phe and 1.29 × 10-4m5/2·mol-1/2·s-1for L-Phe.

Synthesis and Crystal Structure of Cu(II) Complex with 2,9-Bis(n-2',5'-diazaheptanyl)-1,10-phenanthroline

The Cu(II) complex with the ligand 2,9-bis(n-2?5?diazaheptanyl)-1,10-phenan- throline (L) has been synthesized and characterized by single-crystal X-ray diffraction. It crys- tallizes in the monoclinic system, space group P21/n with a = 12.549(4), b = 13.544(4), c = 16.767(5) ? = 107.179(5), C22H32Cl2N6CuO8, Mr = 642.98, V = 2722.5(13) 3, Z = 4, Dc = 1.569 g/cm3, ?= 1.056 mm-1, F(000) =1332, the final R = 0.0733 and wR = 0.1581. The X-ray analysis revealed that the Cu(II) ion is coordinated by six nitrogen atoms of the ligand, in which two nitrogen from phenanthroline and another two from the imine groups near phenanthroline are in the equatorial plane while the two from imine groups at the end of both arms in the axial positions. The coordination geometry can be described as a compressed octahedron.

A Pyridine-copper Inclusion Complex of a New Tripodal Ligand

A pyridine-copper inclusion complex with [Cu(py)4Cl]+ core was prepared in the presence of tripodal ligand tbst {tbst = 1,3,5-tris(2-benzimidazol)sulfanylmethyl-2,4,6-trimethyl- benzene}, and its structure has been determined. It crystallizes in triclinic, space group P with a = 9.0822(2), b = 17.6026(4), c = 18.7156(4) ? a = 93.40, b = 91.2980(1), g = 91.5560(1), V = 2984.81(1) 3, C58H63Cl2CuN11O4S3, Mr = 1208.81, Z = 2, F(000) = 1262, Dc = 1.345 g/cm3, m = 0.615 mm-1, R = 0.0713 and wR = 0.1307 for 7798 observed reflections (I > 2s(I)). X-ray analysis reveals that the uncoordinated tbst and pyridine as guest molecules are included in the complex with formula {[Cu(py)4Cl]Cl}(tbst)(py)4H2O. The tbst, pyridine, aqua and Cl- anion in the com- plex form extensive hydrogen-bonding interactions, building up a quasi-dinuclear structure.

Synthesis and Crystal Structure of the Copper(II) Complex with Tris-(1,10-phenanthroline-5,6-dione)

The title complex [CuL3]（ClO4）2·2H2O·2CH3CN （L = 1,10-phenanthroline-5,6-dione） has been synthesized and characterized by elemental analysis, conductivity, infrared and UV-Vis spectra. X-ray diffraction analysis at room temperature indicates that the complex （C40H28Cl2CuN8O16, Mr = 1011.14） crystallizes in orthorhombic system, space group P212121 with a=13.983（1）, b=14.310（1）, c= 20\^890（2） , V = 4179.7（6） 3, Z = 4, Dc = 1.607 g/cm3, F（000） = 2026,μ（MoKα） = 0.736 mm-1. The final R and wR factors are 0.0446 and 0.1212 respectively with 8545 independent reflections. The title complex is composed of a discrete [CuL3]2+ cation, uncoordinated ClO4- anions, H2O and CH3CN molecules. The central Cu（II） atom is six-coordinated by six nitrogen donors of three ligands. The coordination geometry of Cu（II） could be considered as an approximately ideal octahedral configuration with little static Jahn-Teller distortion （the longest and shortest Cu-N bonds are 2.102 vs 2.139 with the mean length of 2.122 ）, which is very rare for a six-coordinated Cu（II） complex.

Crystal Structure and Molecular Structure of Binuclear Copper(Ⅱ) Complex, [Cu (C_5H_5NO) (C_6H_5COO)_2]_2

At room temperature, dibenzoyl peroxide and pyridine N-oxide reacted with metallic copper powder in a mixed solvent(dichloromethane, trichloromethane and tetrahydrofuran), resulting in a binuclear copper(Ⅱ) complex. [Cu (C_5H_5NO)-(C_6H_5COO)_2]_2. The structure of the complex was characterized by elemental analyses.IR spectra and X-ray single crystal analysis. The crystal is triclinic, space group P1,with cell parameters . a= 9. 262(4) ,b= 10. 697(2) , c=10. 881 (3 )A , a=59. 60( 2 ),β= 74. 83 ( 3 ) .Y = 72. 80 ( 2 )°. V= 880. 0 A￣3 . D_c = 1 . 5 20 g/cm￣3 . Z = 1 . μ= 1 2. 7 cm-1, R=0. 044 ,R_w=0. 048 for 3477 reflections with I>3σ(I), M_r=805. 78. Each copper(Ⅱ) atom is coordinated by four bridging bidentate benzoate ligands and one pyridine M-oxide.

Synthesis and Crystal Structure of Dicyanamide (5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclo- tetradecane) Copper(II) Percholatehydrate

The copper(II) complex [Cu(teta)N(CN)2](ClO4)H2O (teta = 5,7,7,12,14,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized and the crystal structure was determined by single-crystal X-ray diffraction. Crystal data: C18H38ClCuN7O5, monoclinic, space group P21/n, a = 8.796(3), b = 11.885(4), c = 23.054(9) , b = 97.540(4)o, V = 2389.3(15) 3, Mr = 531.54, Z = 4, Dc = 1.478 g/cm3, F(000) = 1124, ?= 1.070 mm-1, the final R = 0.0566 and wR = 0.1162 for 4749 observed reflections (I > 2s(I)). The center copper ion is coordinated by five nitrogen atoms in a square pyramidal geometry, with four from the macrocyclic ligand teta and the other one from a nitrile nitrogen atom of dicyanamide which is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.

Syntheses and Characterizations of Two Copper Coordination Polymers Constructed by 4,4'-Bipyridine

Two new copper coordination polymers [Cu(μ2-4,4?-bipyridine)(NO2)2]n (C10H8- N4O4Cu, Mr = 311.75) 1 and [Cu(μ2-4,4?-bipyridine)2(H2O)2]n?2n(4,4?-bipyridine)?2nClO4?nH2O (C40H38N8O11Cl2Cu, Mr = 941.22) 2 were synthesized by hydrothermal reaction and determined by X-ray diffraction method. Compound 1 crystallizes in monoclinic, space group P2/m with a = 4.7740(10), b = 11.039(2), c = 5.6752(14) ?, β = 91.394(9)o, V = 299.00(11) ?3, Z = 1, Dc = 1.731 g/cm3, F(000) = 157 and μ(MoKa) = 0.7107 mm-1. Compound 2 crystallizes in monoclinic, space group P2/n with a = 12.916(2), b = 11.149(1), c = 15.006(2) ?, β =106.642(6)o, V = 2070.3(5) ?3, Z = 2, Dc = 1.510 g/cm3, F(000) = 970 and μ(MoKa) = 0.7107 mm-1. In the structure of compound 1, the metal atom is in a slightly distorted octahedral CuO4N2 geometry surrounded by four O atoms of two NO2 ligands in the equatorial positions and two N atoms from 4,4?-bipyridine ligands in the axial sites, and the 4,4?-bipyridine ligands bridge the neighboring Cu2+ atoms to form polymeric chains in the lattice. Compound 2 has a 2D square-grid network structure. The square grids are superposed on each other to form a channel framework. The square cavity has dimensions of 11.148(2)? ×11.229(3)?. Every two guest 4,4?-bipyridine molecules are clathra- ted in each hydrophobic host cavity and further stabilized by π-π stacking and hydrogen bonding interactions.

Synthesis and Structure of the Copper(I) Complex Containing Bis(diphenylphosphino)ethane

The mononuclear copper(I) complex, [Cu(dppe)2](PF6)(CH3COCH3) [dppe = bis-(diphenylphosphino)ethane] has been synthesized and characterized by X-ray crystallography. The crystal belongs to monoclinic, Mr=1062.3, space group P21/n with cell parameters a =14.741(2), b =19.354(8), c =18.587(3) ? = 91.41(1)°, V = 5301.5 3, Z = 4, Dc=1.302 g/cm3, F(000)= 2200, = 6.16cm-1, R=0.062, Rw = 0.068. A total of 9679 independent reflections were collected, of which 4574 reflections with I >3σ(I) were observed. The central Cu atom is coordinated by four P atoms from dppe to form a distorted tetrahedral environment. In the coordination sphere the bond lengths of CuP(1), CuP(2), CuP(3) and CuP(4) are 2.298(2), 2.305(2), 2.311(2) and 2.295? respectively; and the PCuP bond angles vary from 87.52(9) to 120.12(9)?

Syntheses and Crystal Structure of [Cu(pyr)_3]·Hg_2I_6

A new compound containing discrete cationic and anionic complexes, [Cu(pyr)3]Hg2I6 (C30H24CuHg2I6N6), where pyr = 2,2-bipyridine, was prepared by the reaction of CuBr with pyr and HgI2 in a mixed solvent of acetone, methanol and acetonitrile. Single-crystal X-ray diffraction analysis indicates that it crystallizes in an orthorhombic system, Pna21 (No. 33), a = 33.1595(7), b = 9.4605(1), c = 13.0899(2) ? V = 4106.4(1) 3, Mr = 1694.67, Dc = 2.741 g/cm3, Z = 4, F(000) = 3012, m(MoKa) = 12.511 mm-1, R = 0.0736, wR = 0.1360 (I > 2(I)) and S = 1.218. The structure consists of discrete [Hg2I6]2- anions and [Cu(bipyridine)3]2+ cations. The double tetrahedral [Hg2I6]2- unit is formed by sharing one tetrahedral edge and possesses approximate D2h symmetry. The mononuclear Cu2+ ion is coordinated by six N atoms from three pyr molecules to form a slightly disordered octahedral geometry.

Synthesis and Structure of a New Copper(II) Complex Cu(C_(13)H_9N_3O_2Br)_2.H_2O

The new copper(II) complex Cu(C13H9N3O2Br)2H2O (N-(2-hydroxy-5-bromo- benzoyl)-N-(picolinylidene)hydrazine is abbreviated as HL ) was obtained from the refluxing solution of Cu(CH3COO)2H2O and HL in the ethanol-N, N-dimethylformamide mix solvent. Crystal data: triclinic, space group P , a = 10.8620(3), b = 11.7453 (3), c = 12.4417(2) ? ?= 62.255(0), ?= 79.097(2), ?= 86.764(2)? V = 1378.52(6) ?, Z = 2, Mr = 719.835, Dc = 1.734 g/cm3, F(000) = 714, (MoK) = 3.739 mm-1, T = 293(2) K, final R = 0.0594 and wR = 0.1416 for 2943 observed reflections with I > 2.0(I). The structure of Cu(C13H9N3O2Br)2H2O has been determined by X-ray analysis and revealed that two L-1 ligands coordinate to the copper(Ⅱ) ion through two oxygen and two nitrogen atoms from the hydrazine groups and two pyridine nitrogen atoms to form an elongated and distorted square-bipyramidal environment for Cu(Ⅱ). The complex is also characterized by 1H NMR spectroscopies