Synthesis and Crystal Structure of [Ni(bdpm)_2(OAc)]_2(N_3)_2·5H_2O(bdpm=Bis(3,5-dimethylpyrazol-1-yl)methane,OAc=CH_3COO~-)

1 INTRODUCTION Bis(pyrazol-1-yl)methane has been one of the po- pular polydentate nitrogen donor ligands due to its strong chelating coordination to transition metal ions as capping ligand. Coordination behavior of the li- gand is able to yield stable M-N-N-C-N-N six-mem- bered boat conformation[1, 2]. The complexes con- taining bdpm ligand have been widely synthesized and characterized in recent years, and exhibit the striking properties in catalysis, magnetism and so on[3-10]. For exa…     

Gold-catalyzed Synthesis of Pyridine Containing Macrocycles, Related to Porphyrin

Porphyrins are very important substances used in a wide range of model systems in many areas, such as biomimic chemistry and material science. This kind of macrocycle generally consists of 5-membered ring to form a cyclic extended aromatic network. Recently much work have been done concerning the modification of porphyrins core structures, and many kinds of analogues have been recorded. One of the important aspects was the research of the porphyrinogen ligand.These macrocycles bear functional resemblance to certain kind of polydentate ligand, and provide a variety of tri-dimensional binding cavities for metal ions. In addition, some other kinds of analogues have been recorded, involving the introduction of a CH unit to replace one of the nitrogen atoms. We also notice the fact that pyridine is a very effective ligand, and it can coordinate with many kinds of metals. Based on these observations, we would like to design and synthesize a new porphyrinogen (5) analogue containing a NNNN core, two of the N atoms from pyrrole and the other two N from pyridine. Such core modifications may alter the electronic structure of the ring and provide variable cavity for metal coordination.     

Synthesis,spectral studies,thermal behavior,and antibacterial activity of Ni(Ⅱ),Cu(Ⅱ),and Zn(Ⅱ) complexes with an ONO tridentate Schiff base

Three new transition metal complexes have been synthesized with a Schiff base,3-(2-hydroxy-5-chlorophenylimino)-l,3- diphenylpropen-1-one.In all complexes Schiff base is completely deprotonated and coordinated to metal as tridentate ligand via phenolic and enolic oxygens and imine nitrogen.Thermal decomposition of the complexes has been studied by thermogravimetry. The in vitro antibacterial activity of Schiff bases and their complexes has been evaluated and compared with the standard drugs.     

Effect of the backbone structure of bidentate ligands in palladium- and nickel-catalyzed polar monomer copolymerization

正Coordination-insertion copolymerization of non-polar olefins and polar monomers by late transition metal catalysts is a powerful method to synthesize functionalized polyolefins[1]. Seminal successes in this copolymerization have been achieved by using group-10 metal catalysts bearing a bidentate ligand such as phosphine-sulfonate and bisphosphine monoxide (BPMO)(Figure 1)[1]. These ligands typically consist of a strongσ-donor and a weakσ-donor and have an arylene linker between the two coordination sites (Figure 1,middle). Although a variety of coordination sites have thus far been investigated, less attention has been paid to the influence of the backbone structure. Recent papers shed light on this issue.     

Synthesis,crystal structures and spectral properties of cobalt (Ⅱ) complexes:[ CoL (N_3) ] ·ClO_4 and CoL (N_3)_2 [L=tris ((3,5-dimethylpyrazol-1-yl) methyl) amine

Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.     

Synthesis and Crystal Structure of a New Chain Coordination Polymer [Cu（inio）2（H2O）]∞ （Inio = Isonicotinic Acid N-Oxide）

1 INTRODUCTION With deep studies on the complex biology system and syntheses of new functional complexes, people have paid more and more attention to the polynuclear complexes. In the construction of one to three dimensional frameworks, multi-dentate ligands are usually used to bridge the metal centers to form polymeric structures[1, 2]. The isonicotinic acid N-oxide can function as a good mono-dentate ligand[3～8] through one oxygen atom from the group of -NO or carboxyl, and the dep…     

Structural Determination of Bis-histidinopeptide Zinc Complexes by 15N NMR (HMBC) Spectra

Polynitrogen receptors such as bis-histidine peptides possess strong ability to bind metals, which play much important roles in medicinal, bioinorganic, bioorganic, biomimetic and supramolecular chemistry. In order to investigate the interaction of these hosts with a variety of neutral, cationic and anionic guests, several techniques, for example, NMR,potentiometric tirations and monocrystal X-ray diffraction have been employed. Among them NMR is a powerful technique for unraveling the structure of polynitrogen receptors as long as they are in solution where the rapid tumbling of molecules averages out the anisotropies such as chemical shift and dipole-dipole interactions. General 1H NMR approach has been widely used for the study of host-guest interaction, but it is difficult for the accurate measurement in complexes structures, particularly metal complexes structures in which how the polynitrogen receptors bind metal, and which nitrogen binds metal and so on.     

1D Lanthanide Coordination Polymers Based on 3-（Pyridin-4,yl）benzoic Acid： Syntheses, Structures and Luminescent Properties

Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(H2O)2· H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoclinic system, space group P1. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.     

Synthesis and Crystal Structure of the Novel Chiral o—Hydroxyphenyloxazoline Metal Complexes

1 INTRODUCTION Optically active oxazolines have been extensi- vely used as valuable chiral ligands for transition metals in asymmetric catalysis[1]. The design and syntheses of new chiral oxazoline ligands have inspired many scientists to work with great efforts during the recent years. Our interest has been focus- ed on the studies of enantioselective transition- metal catalysis of heterocyclic ligands. In the pre- sent work, we choose o-hydroxyphenyloxazoline ligand for it has a rigi…     

Synthesis,Crystal Structure and Nonlinear Optical Properties of Nickel（Ⅱ） Complex with Schiff—base Ligand

1 INTRODUCTION Recently, the transition metal complexes and inorganic clusters have also been investigated as promising nonlinear optical materials[1～3]. In our past work, much more efforts have been made to find potential nonlinear optical derived from thiosemicarbazone and dithio-carbazates[4]. As a continuous study on new nonlinear optical materials among the -electron delocalized systems con- taining mixed sulfur and nitrogen donors[5, 6], we report herein the crystal structure and…     

Synthesis, Structure and Photo- luminescence of Cu[（PPh3）2]（acac） （PPh3 = Triphenylphosphine, acac = Acetylacetone）

A novel complex Cu(PPh3)2(acac) 1 (PPh3 = triphenylphosphine, acac = acetylacetone) was obtained by a solution reaction and structurally characterized by X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 13.7361(8), b = 12.8204(7), c = 19.7638(13) , β = 95.946(2)°, C41H37CuO2P2, Mr = 687.19, V = 3461.7(4) 3, Z = 4, Dc = 1.319 g/cm3, S = 1.067, μ(MoKα) = 0.758 mm–1, F(000) = 1432, R = 0.0403 and wR = 0.0990. Complex 1 is characterized by an isolated structure. X-ray structure analysis of 1 shows that acac behaves as a chelating ligand and PPh3 coordinates as a monodentate ligand to the Cu(I) atoms. Photoluminescent investigation reveals that the title complex displays a strong green-light emission.     

Synthesis and magnetic properties of heterometal cyclic tetranuclear complexes [Cu(II)LM(II)(hfac)]2 (M(II) = Zn,Cu, Ni,Co, Fe,Mn; H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane; Hhfac = hexafluoroacetylacetone)

A series of heterometal cyclic tetranuclear complexes [Cu(II)LM(II)(hfac)](2) (M(II) = Zn (1), Cu (2), Ni (3), Co (4), Fe(5), and Mn (6)) have been synthesized by the assembly reaction of K[CuL] and [M(II)(hfac)(2)(H(2)O)(2)] with a 1:1 mole ratio in methanol, where H(3)L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane and Hhfac = hexafluoroacetylacetone. The crystal structures of 2, 4, and [Cu(II)LMn(II)(acac)](2) (6a) (Hacac = acetylacetone) were determined by single-crystal X-ray analyses. Each complex has a cyclic tetranuclear Cu(II)(2)M(II)(2) structure, in which the Cu(II) complex functions as a "bridging ligand complex", and the Cu(II) and M(II) ions are alternately arrayed. One side of the planar Cu(II) complex coordinates to one M(II) ion at the two phenoxo and the methoxy oxygen atoms, and the opposite side of the Cu(II) complex coordinates to another M(II) ion at the amido oxygen atom. The temperature-dependent magnetic susceptibilities revealed spin states of S(M) = 0, 1/2, 1, 3/2, 2, and 5/2 for the Zn(II), Cu(II), Ni(II), Co(II), Fe(II), and Mn(II) ions, respectively. Satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a rectangular arrangement with two different g-factors for the Cu(II) and M(II) ions, two different isotropic magnetic exchange interactions, J(1) and J(2), between the Cu(II) and M(II) ions, and a zero-field splitting term for the M(II) ion. In all cases, the antiferromagnetic coupling constants were found for both exchange interactions suggesting nonzero spin ground states with S(T) = 2/S(M) - S(Cu)/, which were confirmed by the analysis of the field-dependent magnetization measurements.     

Synthesis and Crystal Structure of Copper(Ⅱ)Complex with N-Acetoxyl-picolinamide

Using Cu(Ⅱ) as the template, a complex {[Cu2L2(H2O)2] 4H2O}n (L = N-acetoxyl- picolinamide) has been successfully synthesized and characterized by single-crystal X-ray diffrac tion. The crystal is of monoclinic, space group C2/c, with a = 24.144(5), b = 7.1622(14), c = 17.283(4) (A), C16H24Cu2N4O12, Mr = 591.47, β = 131.73(3)°, V = 2230.3(8) (A)3, Z = 4, Dc= 1.761 g/cm3, F(000) = 1208,μ = 1.978 mm-1, R = 0.0400 and wR = 0.1099. The copper (Ⅱ) ion is five coordinated with a distorted square pyramidal geometry. The complex can be viewed as a one dimensional chain structure by carboxylic bridges among copper atoms. In the complex there exist hydrogen bonding interactions to stabilize the structure.     

Reactivity of rhenium(V) oxo Schiff base complexes with phosphine ligands: rearrangement and reduction reactions

The symmetric rhenium(V) oxo Schiff base complexes trans-[ReO(OH2)(acac2en)]Cl and trans-[ReOCl(acac2pn)], where acac2en and acac2pn are the tetradentate Schiff base ligands N,N'-ethylenebis(acetylacetone) diimine and N,N'-propylenebis(acetylacetone) diimine, respectively, were reacted with monodentate phosphine ligands to yield one of two unique cationic phosphine complexes depending on the ligand backbone length (en vs pn) and the identity of the phosphine ligand. Reduction of the Re(V) oxo core to Re(III) resulted on reaction of trans-[ReO(OH2)(acac2en)]Cl with triphenylphosphine or diethylphenylphosphine to yield a single reduced, disubstituted product of the general type trans-[Re(III)(PR3)2(acac2en)]+. Rather unexpectedly, a similar reaction with the stronger reducing agent triethylphosphine yielded the intramolecularly rearranged, asymmetric cis-[Re(V)O(PEt3)(acac2en)]+ complex. Reactions of trans-[Re(V)O(acac2pn)Cl] with the same phosphine ligands yielded only the rearranged asymmetric cis-[Re(V)O(PR3)(acac2pn)]+ complexes in quantitative yield. The compounds were characterized using standard spectroscopic methods, elemental analyses, cyclic voltammetry, and single-crystal X-ray diffraction. The crystallographic data for the structures reported are as follows: trans-[Re(III)(PPh3)2(acac2en)]PF6 (H48C48N2O2P2Re.PF6), 1, triclinic (P), a = 18.8261(12) A, b = 16.2517(10) A, c = 15.4556(10) A, alpha = 95.522(1) degrees , beta = 97.130(1) degrees , gamma = 91.350(1) degrees , V = 4667.4(5) A(3), Z = 4; trans-[Re(III)(PEt2Ph)2(acac2en)]PF6 (H48C32N2O2P2Re.PF6), 2, orthorhombic (Pccn), a = 10.4753(6) A, b =18.4315(10) A, c = 18.9245(11) A, V = 3653.9(4) A3, Z = 4; cis-[Re(V)O(PEt3)(acac2en)]PF6 (H33C18N2O3PRe.1.25PF6, 3, monoclinic (C2/c), a = 39.8194(15) A, b = 13.6187(5) A, c = 20.1777(8) A, beta = 107.7730(10) degrees , V = 10419.9(7) A3, Z = 16; cis-[Re(V)O(PPh3)(acac2pn)]PF6 (H35C31N2O3PRe.PF6), 4, triclinic (P), a = 10.3094(10) A, b =12.1196(12) A, c = 14.8146(15) A, alpha = 105.939(2) degrees , beta = 105.383(2) degrees , gamma = 93.525(2) degrees , V = 1698.0(3) A3, Z = 2; cis-[Re(V)O(PEt2Ph)(acac2pn)]PF6 (H35C23N2O3PRe.PF6), 5, monoclinic (P2(1)/n), a = 18.1183(18) A, b = 11.580(1) A, c = 28.519(3) A, beta = 101.861(2) degrees , V = 5855.9(10) A(3), Z = 4.     

Synthesis and characterization of novel rhenium(V) tetradentate N2O2 Schiff base monomer and dimer complexes

Several rhenium(V) oxo complexes with tetradentate N(2)O(2) Schiff base ligands were synthesized and characterized. The general synthetic procedure involved reaction of [NBu(4)][ReOCl(4)] with a tetradentate Schiff base ligand (L(1) = N,N'-ethylenebis(acetylacetoneimine), (acac(2)en) or L(2) = N,N'-propylenebis(acetylacetoneimine) (acac(2)pn)) in ethanol solution to generate complexes of the form trans-ReOX(L) where X = Cl(-), MeO(-), ReO(4)(-), or H(2)O. The product isolated from the reaction was found to be dependent on the reaction conditions, in particular the presence or absence of water and/or base. The mu-oxo-Re(2)O(3)(L)(2) dimers were synthesized and characterized for chemical and structural comparison to the related monomers. Conversion of the monomer to its dimer analogue was followed qualitatively by spectrophotometry. The complexes were characterized by (1)H and (13)C NMR, UV-vis, and IR spectroscopy, elemental analysis, and single crystal X-ray diffraction. The crystallographic data reported for the structures are as follows: trans-[ReO(OH(2))(acac(2)en)]Cl (H(20)C(12)ClN(2)O(4)Re) 1, triclinic (Ponemacr;), a = 7.2888(6) A, b = 9.8299(8) A, c = 10.8195(9) A, alpha = 81.7670(10) degrees, beta = 77.1510(10) degrees, gamma = 87.6200(10) degrees, V = 747.96(11) A(3), Z = 2; trans-[ReO(OReO(3))(acac(2)en)] (H(18)C(12)N(2)O(7)Re(2)) 2, monoclinic (P2(1)/c), a = 7.5547(4) A, b = 8.7409(5) A, c= 25.7794(13) A, beta = 92.7780(10) degrees, V = 1700.34(16) A(3), Z = 4; trans-[ReOCl(acac(2)pn)] (H(20)C(13)N(2)O(3)ClRe) 3, monoclinic (P2(1)/c), a = 8.1628(5) A, b = 13.0699(8) A, c = 28.3902(17) A, beta = 97.5630(10) degrees, V = 3002.5(3) A(3), Z = 8; trans-[ReO(OMe)(acac(2)pn)] (H(23)C(14)N(2)O(4)Re) 4, monoclinic (P2(1)/c), a = 6.7104(8) A, b = 27.844(3) A, c = 8.2292(9) A, beta = 92.197(2) degrees, V = 1536.4(3) A(3), Z = 4; trans-[mu-oxo-Re(2)O(3)(acac(2)en)(2)] (H(36)C(24)N(4)O(7)Re(2)) 5, monoclinic (P2(1)/n), a = 9.0064(5) A, b = 12.2612(7) A, c = 12.3695(7) A, beta = 90.2853(10) degrees, V = 1365.94(13) A(3), Z = 2; and trans-[mu-oxo Re(2)O(3)(acac(2)pn)(2)] (H(40)C(26)N(4)O(7)Re(2)) 6, monoclinic (P2(1)/n), a = 9.1190(5) A, b = 12.2452(7) A, c = 12.8863(8) A, beta = 92.0510(10) degrees, V = 1438.01(14) A(3), Z = 2.     

Synthesis and Structural Characterization of Four Zinc Complexes Containing 3,5‐Dimethylpyrazole and Carboxylate Ligands

Four new zinc(II) complexes Zn₂(μ‐dmpz)₂(Hdmpz)₂(L1)₂ ( 1 ) (Hdmpz = 3,5‐dimethylpyrazole, HL1 = 2‐methyl‐2‐phenoxypropanoic acid), Zn(Hdmpz)₂(L2)₂ ( 2 ) [HL2 = 2‐hydroxy‐5‐(phenyldiazenyl)benzoic acid], Zn₂(μ‐dmpz)₂(Hdmpz)₂(L3)₂ ( 3 ) [HL3 = 3,4‐(methylenedioxy)benzoic acid], and Zn₂(μ‐dmpz)₂(Hdmpz)₂(L4)₂ ( 4 ) [HL4 = 3‐(4‐methoxyphenyl)acrylic acid] were prepared and structurally characterized by different techniques including elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction analysis. The X‐ray studies suggested that all these complexes except compound 2 are centrosymmetric dinuclear complexes with a tetrahedral arrangement around each zinc ion, whereas compound 2 is a mononuclear complex. The pyrazole ligand is coordinated in both terminal as well as a bridging fashion in the dinuclear moiety, whereas the pyrazole ligand in compound 2 is coordinated only in monodentate terminal fashion with its neutral nitrogen group. In all four complexes the carboxylate functions behave as monodentate ligands. All complexes show intramolecular hydrogen bonding of N–H ··· O between N–H of pyrazole and nonbonded oxygen atom of carboxylate. Furthermore, rich intermolecular weak interactions such as classical hydrogen bonds, C–H ··· O, C–H ··· N, C–H ··· π, and CH₃–π interactions exist and complexes 1 – 4 display a set of 3D superamolecular frameworks. In addition, the four compounds are thermally stable below 150 °C.     

Synthesis and Crystal Structure of a Hydrogen-bonded Supramolecular Compound [(C_6H_5N_2O)_3·Cu_1._5]·6H_2O

1 INTRODUCTION The binding of metal ions by proteins and pep- tides is of fundamental interest due to the impor- tance of metal ions in biological systems. Metals may be part of the active sites of enzymes, stabilize the macromolecular structure of proteins and affect enzymes or membranes to control cell metabolism[1]. Therefore, for many years there has been a great in- terest in the study of complexes able to mimic these active sites of metalloproteins. In this case, metal complexes of…     

Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ)Complex with 4,4',6,6'-Tetrabromo-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol

A new mononuclear Cu(Ⅱ)complex,[Cu(L)](H2L=4,4',6,6'tetrabromo-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol),has been synthesized and structurally characteri-zed.X-ray crystal stucture of the complex reveals that the Cu(Ⅱ)ion is four-coordinated by two oxygen atoms and two nitrogen atoms from L2-unit.Crystallographic data:monoclinic,space group P21/n with a=14.076(2),b=6.9801(14),c=19.858(2)(A),β=107.613(2)°,C16H10Br4CuN2O4,Mr =677.44,V=1859.6(5)(A)3,Dc=2.420 g/cm3,μ=9.796 mm-1,F(000)=1284,Z=4,the final R=0.0516 and wR=0.0938 for 1879 observed reflections with I＞20(I).The dihedral angel between the two coordination planes of Cu(1)-N(2)-O(4)and Cu(1)-N(1)-O(3))is 30.08(6)°.     

Synthesis and Crystal Structure of Binuclear Copper （Ⅱ） Complex Containing （Dimethylaminomethyl）ferrocene

1 INTRODUCTION Transition metal complexes with ferrocene are of considerable interest in the past fifty years because of their novel structures and special properties[1, 2]. The chemistry of ferrocene and its derivatives has become richer and richer in the last decade. Many complexes containing ferrocenyl have been synthesized and characterized[3～5]. Recently we have reported the synthesis and crystal structure of dibromo[1,1?bis(diphenylphosphino)- ferrocene]cadmium (Ⅱ)[6]. Herein we…     

Synthesis and Crystal Structure of Copper(II) Complex with N-Acetoxyl-picolinamide

1 INTRODUCTION The picoloylhydrazide compounds are close to thebiologic environment and can react with microele-ments in organism so as to have antitubercular andantineoplastic activities. However, owing to the exis-tence of amino group, this kind of compounds aretoxic to some extent[1]. In order to decrease theirtoxicity, hydrazone or hydrazide compounds synthe-sized by the condensation reaction of amino and car-bonyl groups have been well studied in recentyears[1～7]. Herein we report t…