Synthesis and Structure of the Copper(Ⅰ) Complex [Cu(PPh3)2(BH4)]

Mononuclear copper( Ⅰ ) complex [Cu(PPh3)2(BH4)] has been synthesized by ligand replacement reaction in methanol and characterized by elemental analyses, molecular weight determination, IR spectra and X-ray single crystal analysis,its conductivity has also been measured. The crystal is monoclinic, space group C2/c, a =24.776(4), b=9.173(7), c=15.564(2)A; β=116.10(1)°, V=3176.73 A3, Z =4, F(000)=1256, μ(MoKα)=8.11 cm-1, Dc=1. 26 g/cm3, M=602.79, R=0. 039, Rw= 0. 050. The results show that PPh3 coordinates as monodentate ligand to the Cu ( Ⅰ ) atoms, and BH4 behaves as a bidentate ligand in the prepared complex.The central copper atom belongs to tetrahedron coordination geometry.     

Synthesis, Characterization and Crystal Structure of a Diiron Azadithiolate Complex [（μ-SCH2）2NCH2Ph]Fe2（CO）5（PPh3）

Treatment of complex [(μ-SCH 2) 2 NCH 2 Ph]Fe 2 (CO) 6 with PPh 3 in the presence of decarbonylating agent Me 3 NO·2H 2 O afforded the title complex [(μ-SCH 2) 2 NCH 2 Ph]Fe 2 (CO) 5 (PPh 3) in 70% yield.The new complex was characterized by elemental analysis,IR,and 1 H (31 P,13 C) NMR spectroscopic techniques as well as by X-ray crystallography.It crystallizes in triclinic,space group P 1 with a=9.3016(19),b=12.698(3),c=13.904(3),V=1519.8(7)3,Z=2,C 32 H 26 Fe 2 NO 5 PS 2,M r=711.33,D c=1.554 g/cm 3,μ(MoKα)=1.187 mm-1,F(000)=728,T=113(2) K,the final R=0.0288 and wR=0.0680 for 3982 observed reflections (I > 2σ(I)).The PPh 3 ligand resides in an axial position of the square-pyramidal geometry of the neighboring Fe atom and trans to the benzene ring in order to minimize the steric repulsion between PPh 3 and the benzene ring.     

Synthesis,Crystal Structure and Photophysical Properties of Cu（Ⅰ） Complexes Containing 2,5-Bis（pyridyl）-1,3,4-oxadiazole

Four novel Cu(Ⅰ) complexes,[Cu(o-PYO)(PPh3)2]BF4(1),[Cu(o-PYO)(DPEphos)]BF4(2),[Cu2 (o-PYO)(PPh3)3(CH3CN)](BF4)2(3) and [Cu2(o-PYO)(DPEphos)2 ](BF4)2(4) (o-PYO=2,5bis(pyridyl)-1,3,4-oxadiazole,PPh 3=triphenylphosphine,DPEphos=bis(2-(diphenylphosphanyl)phenyl)ether),have been synthesized and characterized by 1 H NMR,elemental analysis and single-crystal X-ray diffraction.The central cuprous ions in all complexes are surrounded by N and P atoms to form a distorted tetrahedral geometry,although one of the cuprous ions in complex 3 is coordinated by a PPh3 and an acetonitrile molecule due to the steric hindrance and weak coordination ability from monodentate PPh3 ligand.The UV-vis absorption spectra in CH2Cl2 show the characteristic metal-to-ligand charge transfer (MLCT) absorption bands in the region of 360-480nm.Four Cu(I) complexes exhibit yellow to orange-red phosphorescence with the emission maximum at 572,577,562 and 597nm,respectively in the solid state.     

A Cu(II) Complex with IM-MeImz-κ~2 N,O Mode in [Cu(IM-MeImz)_2]·(SCN)_2: Synthesis, Crystal Structure and Magnetic Properties

A new copper(II) compound with imino nitroxide radicals [Cu(IM-MeImz)2]?(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12) , β = 105.0290(10)o, V = 1552.25(19) 3, C24H34CuN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) = 650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(II) ion as an unusual didentate chelate with a κ2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(II) are occupied by two O and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(II) ion and radicals.     

Synthesis and Structure of a Novel Copper（Ⅱ） Dinuclear Complex with 4,4′-Dipyridyl as the Bridge

With N,N′-bis(benzimidazol-2-methyl)amine as the ligand,a novel Cu(Ⅱ) dinuclear complex was synthesized as a mimetic compound of superoxide dismutase(SOD).The complex was characterized with element analysis,UV and IR spectra.The crystal structure was determined by using X-ray diffraction analysis.the crystal structure shows that Cu(Ⅱ) and its coordinated atoms construct distorted octahedron configuration with oxygen atome of (ClO4-)s in the axial directions.The coordinated cations are linked by (ClO4-)s to form nonplanar sheets.All sheets are linked together into three-dimensional network by the intermolecular hydrogen bonds.The result of the activity assay indicates that the complex does have certain biological activity.     

Synthesis and Crystal Structure of a Novel Binuclear Copper（Ⅱ） Complex, [Cu（paba）Cl]

A novel binuclear Cu（Ⅱ） complex [Cu（paba）Cl] （pabaH = 2-（2-pyridylmethylimine）benzenesulfonic acid） has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal of the title complex crystallizes in a monoclinic system, space group P21/n, with a = 6.8165（7）, b = 15.3073（16）, c = 12.3795（13） A^°, β= 95.0160（10）°, V= 1286.8（2） A^°^3, Mr = 360.26, Dc= 1.860 g/cm^3,μ = 2.074 mm^-1, F（000） = 724, Z = 4, the final R = 0.0252 and wR = 0.0675 for 2395 observed reflections with I 〉 20（I）. The title complex is centrosymmetric and a pair of chlorides act as μ2-bridges to link two Cu（Ⅱ） ions forming a binuclear complex. Every Cu（Ⅱ） ion is five-coordinated by pyridyl N, imine N and sulfonate O atoms of the tridentate paba ligand as well as two bridging Cl^-, constructing the distorted square-pyramidal geometry. In the structure extensive hydrogen bonds and weak π-π stacking stabilize the solid structures, through which the complex builds its 3-dimensional supramolecular structure.     

In Situ Hydrothermal Synthesis of a Mononuclear Copper（Ⅱ） Complex： Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-Hydroxyl-5-sulfoisophthalic Acid）

The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.     

Synthesis and Crystal Structure of[Cu（dppb）（NO_3）]_2（dppb=1,4-Bis（diphenylphosphino）butane）

The synthesis and molecular structure of a new dinuclear copper(Ⅰ) complex [Cu(dppb)(NO 3)] 2 are reported.The compound crystallizes in the monoclinic system,space group P2 1 /n with a=12.830(3),b=10.899(2),c=19.666 (4),β=104.69(3)°,V=2660.1(9)3,Z=4,D c=1.378 g/cm 3,F(000)=1144,the final R=0.0600 and wR=0.0668 for 2951 observed reflections with I > 2σ(Ⅰ).The complex contains a folded Cu 2 P 4 core structure,with two Cu(Ⅰ) atoms being bridged by a pair of dppb ligands to form a 14-membered Cu 2 P 4 C 8 zigzag ring.The ligand sphere of each metal center is completed by a nitrate anion in a chelating fashion.     

Synthesis, Crystal Structure and Ferromagnetic Properties of a New Dicyanamide Bridged Dicopper(Ⅱ) Complex with IM-1''-MeBzIm-κ2 N, O Mode

A new dinuclear copper(Ⅱ) complex with imino nitroxide radicals [Cu2(NO3)2(IM-1'-MeBzlm)2(dca)2] (IM-1'-MeBzlm = 2-{2'-[(1'-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimi-dazoline-1-oxyl, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinie, space group P1, with a =9.440(5), b = 10.124(6), c = 11.603(7)(A°), α= 102.904(7),β = 94.033(6), γ= 104.299(7)°,C34H40Cu2N16O8, Mr= 927.90, V= 1038.2(10) (A°)3, Z = 1, Dc=1.484 g/cm3,μ(MoKα) = 1.093 mm-1,F(000) = 478, R = 0.0609 and wR = 0.1512 for 2889 observed reflections with I > 2σ(I). X-ray analysis reveals that two Cu(Ⅱ) atoms are bridged by two dicyanamides to form a centrosymmetric Cu(Ⅱ)-Cu(Ⅱ) dinuclear entity. Every Cu(Ⅱ) ion is five-coordinated with a distorted square pyramidal coordination geometry and IM-1'-MeBzlm ligand coordinates to the metal ion with the κ2 N(1'-MeBzlm), O(IM) mode to avoid steric hindrance with the methyl group in the complex. Meanwhile, the molecules are linked by intermolecular hydrogen bonds, leading to a 1-D chain structure. Moreover, such chains are further linked by π-π stacking interactions to form a 2-D network structure. Magnetic measurement demonstrates that the intramolecular exchange couplings between Cu(Ⅱ) ion and the IM-1'-MeBzlm are ferromagnetic with J = 12.46 cm-1, where the spin Hamitonian is defined as H= -2JS1S2 within the complex.     

Synthesis,Crystal Structure and Ferromagnetic Properties of a New Dicyanamide Bridged Dicopper(Ⅱ) Complex with IM-1′-MeBzIm-κ2 N,O Mode

A new dinuclear copper(Ⅱ) complex with imino nitroxide radicals [Cu2(NO3)2(IM-1′-MeBzIm)2(dca)2] (IM-1′-MeBzIm = 2-{2′-[(l′-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimi-dazoline-1-oxyl, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinic, space group P1, with a = 9.440(5), b = 10.124(6), c = 11.603(7), α = 102.904(7), β = 94.033(6), γ = 104.299(7)°, C34H40Cu2N16O8, Mr = 927.90, V = 1038.2(10) 3, Z = 1, Dc = 1.484 g/cm3, μ(MoKα) = 1.093 mm-1, F(000) = 478, R = 0.0609 and wR = 0.1512 for 2889 observed reflections with I > 2σ(I). X-ray analysis reveals that two Cu(Ⅱ) atoms are bridged by two dicyanamides to form a centrosymmetric Cu(Ⅱ)-Cu(Ⅱ) dinuclear entity. Every Cu(Ⅱ) ion is five-coordinated with a distorted square pyramidal coordination geometry and IM-1′-MeBzIm ligand coordinates to the metal ion with the κ2 N(1′-MeBzIm), O(IM) mode to avoid steric hindrance with the methyl group in the complex. Meanwhile, the molecules are linked by intermolecular hydrogen bonds, leading to a 1-D chain structure. Moreover, such chains are further linked by π-π stacking interactions to form a 2-D network structure. Magnetic measurement demonstrates that the intramolecular exchange couplings between Cu(Ⅱ) ion and the IM-1′-MeBzIm are ferromagnetic with J = 12.46 cm-1, where the spin Hamitonian is defined as■ = -2J12 within the complex.     

Synthesis and Crystal Structure of a Dinuclear Compound Cu2[(O=PPh2)2N]2(μ-O2PPh2)2

A neutral dinuclear compound Cu2[(O=PPh2)2N]2(μ-O2PPh2)2 has been unexpec- tedly prepared from the reaction of [Cu2(dppa)2(MeCN)4](ClO4)2 (dppa = bis(diphenylphosphino)- amine) and Sn(edt)2 (edt = ethane-1,2-dithiolate) in dichloromethane in air. ESR spectrum shows that the original Cu+ ion has been oxidized. The crystal structure determined by an X-ray single diffrac- tometer displays that the concurrence of the redox and hydrolysis of the origin ligand dppa is taken with the formation of two new ligands. The complex crystallizes in triclinic, space group P with a = 9.4269(13), b = 10.7522(13), c = 16.787(2)(A), ( = 92.042(5), β = 104.591(7), γ = 96.167(6)°, V = 1633.6(4)(A)3, C72H60 Cu2N2O8P6, Mr = 1394.12, Z = 1, Dc = 1.419 g/cm3, F(000) = 718, μ = 0.856 mm-1, the final R = 0.0530 and wR = 0.1096 for 4210 observed reflections with I > 2σ(I).     

新型一维双席夫碱铜(Ⅰ)配合物的合成、结构及荧光性质(英)

在室温下，[Cu(PPh₃)₂(CH₃CN)₂]ClO₄和双席夫碱配体1，2-双(3′-吡啶基亚甲基氨基)乙烷(L)反应得到一个新型化合物[Cu(PPh₃)(L)](ClO₄) (1)。结构分析表明该化合物属于单斜晶系，空间群为P2₁ /n，晶胞参数为a=1.696 6(16)     

Structural, dynamic, and theoretical studies of [AunPt2(PPh3)4(mu-S)2-n(mu 3-S)nL][PF6]n [n = 1, L = PPh3; n = 2, L = Ph2PCH2PPh2, (C5H4PPh2)2Fe

Three heterometallic Au-Pt complexes [Pt2(PPh3)4(mu-S)(mu 3-S)Au(PPh3)][PF6] (2), [Pt2(PPh3)4(mu 3-S)2Au2(mu-dppm)]-[PF6]2 (3), and [Pt2(PPh3)4(mu 3-S)2Au2(mu-dppf)][PF6]2 (4) have been synthesized from Pt2(PPh3)4(mu-S)2 (1) [dppm = Ph2PCH2PPh2; dppf = (C5H4PPh2)2Fe] and characterized by single-crystal X-ray crystallography. In 2, the Au(I) atom is anchored on only one of the sulfur centers. In 3 and 4, both sulfur atoms are aurated, showing the ability of 1 to support an overhead bridge structure, viz. [Au2(P-P)], with or without the presence of Au-Au bond. The change of dppf to dppm facilitates such active interactions. Two stereoisomers of complex 3 (3a,b) have been obtained and characterized by single-crystal X-ray crystallography. NLDFT calculations on 2 show that the linear coordination mode is stabilized with respect to the trigonal planar mode by 14.0 kJ/mol. All complexes (2-4) are fluxional in solution with different mechanisms. In 2, the [Au(PPh3)] fragment switches rapidly between the two sulfur sites. Our hybrid MM-NLDFT calculations found a transition state in which the Au(I) bears an irregular trigonal planar geometry (delta G++ = 19.9 kJ/mol), as well as an intermediate in which Au(I) adopts a regular trigonal planar geometry. Complexes 3a,b are roughly diastereoisomeric and related by sigma (mirror plane) conversion. This symmetry operation can be broken down to two mutually dependent fluxional processes: (i) rapid flipping of the dppm methylene group across the molecular plane defined by the overhead bridge; (ii) rocking motion of the two Au atoms across the S...S axis of the (Pt2S2) core. Modeling of the former by molecular mechanics yields a steric barrier of 29.0 kJ/mol, close to that obtained from variable-temperature 31P(1Hz) NMR study (33.7 kJ/mol). In 4, the twisting of the ferrocenyl moiety across the S...S axis is in concert with a rocking motion of the two gold atoms. The movement of dppf is sterically most demanding, and hence, 4 is the only complex that shows a static structure at lower temperatures. Pertinent crystallographic data: (2) space group P1, a = 15.0340(5) A, b = 15.5009(5) A, c = 21.9604(7) A, alpha = 74.805(1) degrees, beta = 85.733(1) degrees, gamma = 78.553(1) degrees, R = 0.0500; (3a) space group Pna2(1), a = 32.0538(4) A, b = 16.0822(3) A, c = 18.9388(3) A, R = 0.0347; (3b) space group Pna2(1), a = 31.950(2) A, b = 16.0157(8) A, c = 18.8460(9) A, R = 0.0478; (4) space group P2(1)/c, a = 13.8668(2) A, b = 51.7754(4) A, c = 15.9660(2) A, beta = 113.786(1) degrees, R = 0.0649.     

Conformational analysis of triphenylphosphine in square planar organometallic complexes: [(PPh(3))(ML(1)L(2)L(3))] and [M(acac)(L')(PPh(3))

The conformation analysis of free PPh(3) and PPh(3) coordinated to tetrahedral, trigonal-bipyramidal, octahedral or square planar achiral metal centres is discussed. Results from ADF calculations, in agreement with experimental structures, show that favoured degenerate conformations of complex-bound PPh(3) in square planar [(PPh(3))(ML(1)L(2)L(3))] and [M(acac)(L')(PPh(3))] complexes can be obtained by applying the following principles (P helicity, view along P-M axis), (i) superimpose C(ortho) of the vertical ring A onto the nadir plane perpendicular to the square plane and allow ring A to tilt towards the smallest ligand, (ii) allow ring B to tilt in the space below the smallest ligand in the quadrant between the nadir plane below the complex and a horizontal plane through the SQP of the complex, (iii) tilt ring C over the largest ligand and (iv) allow correlated tilting of rings A, B and C to minimize inter ring-ring and inter ring-ligand interactions.     

水杨醛缩4-氨基安替吡啉双核铜(Ⅱ)配合物的合成和晶体结构

标题化合物{[Cu(C18H17N3O2)]2(COO)}(ClO4).3H2O(1)由Cu(ClO4)2.6H2O\甲酸、水杨醋缩4-氨基安替吡啉经溶剂热反应得到,用单晶衍射法测定了配合物的结构,具体测定结果如下:单斜晶,空间群P2/c,a=15.1500(2),b=23.8857(11),c=12.9709(4),β=107.265(3)°,V=4482.3(3)3,Dc=1.349g/cm3,Z=4,Mr=910.28,μ=1.066mm-1和F(000)=1872,最终偏差因子分别为R1=0.0924,wR2=0.2514。在此晶体结构中,2个铜离子被COO-和苯酚氧桥联形成二聚单元,每个Cu(Ⅱ)是五配位的变形四方锥构型。     

Syntheses and Structural Characterizations of [Co~Ⅲ(TPA)(N_3)_2]·(ClO_4) and [Cu~Ⅱ(TPA)(N_3)]·(ClO_4) (TPA=Tris(2-pyridylmethyl)amine)

1 INTRODUCTION As a versatile ligand, N3- has been attracted great interest for several decades. In addition to mono- dentate coordination through a single N-donor, the azide group is not only an efficient antiferromag- netic coupler in the 1,3-fashion…     

First paramagnetic 4d transition-metal complex with a redox-active tetrathiafulvalene derivative, [Ru(salen)(PPh3)(TTF-CH=CH-Py)]BF4 [salen(2-) = N,N'-ethan-1,2-diylbis(salicylidenamine), PPh3 = triphenylphosphine, TTF-CH=CH-Py = 4-(2-tetrathiafulvalenylethenyl)pyridine

The first paramagnetic 4d transition-metal complex with a redox-active tetrathiafulvalene ligand has been synthesized. The preparation, X-ray structure, electrochemistry, and electron paramagnetic resonance measurements of [Ru(salen)(PPh3)(TTF-CH=CH-Py)](BF4) [1(BF4)] are reported. The crystal structure reveals that the paramagnetic Ru(III) (s = 1/2) center is in a tetragonally elongated octahedral geometry and the TTF-CH=CH-Py ligand is coordinated to the axial position of the Ru(III) ion through the nitrogen atom of the pyridine group. Thus, 1(BF4) is an attractive precursor to study future pi-4d interactions in dual-property conducting and magnetic materials.