A New Layer W/Cu/S Polymer with Heterobimetallic Nodes and Tridentate Trithiocyanuric Acid

Solvothermal reaction of [WS4]2-with CuCN and trithiocyanuric acid（L1） in orga-nic solvents gave rise to a new W/Cu/S polymer with a 2D anionic network,namely [Et4N]2[WS4Cu3（C3N3S3H1.5）2]（1）.The anionic layer of 1 is constructed by the T-shaped {WS4Cu3} subunits as nodes and L1 as linkers and features a（4,4） topology.Both 1 and its isomorphous compound [Et4N]2[MoS4Cu3（C3N3S3H1.5）2]（2） have been fully characterized by X-ray crystal analysis,IR and microanalyses.Compounds 1 and 2 show optical transitions with band gaps of 2.17 and 1.84 eV,respectively.

A Novel 3D Heterobimetallic Cyano-bridged Coor- dination Polymer {(NH_4)_2[Cd(H_2O)Fe(CN)_6]}_n:Synthesis and Crystal Structure

A novel heterobimetaUic coordination polymer, {（NH4）2[Cd（H20）Fe（CN）6]}n 1, has been synthesized by using the slow diffusion method and structurally characterized by elemental analysis, 1R spectroscopy and single-crystal X-ray diffraction. The crystal crystallizes in the monoclinic system, space group P21/n, a = 7.4202（16）, b = 14.939（3）, c = 10.868（2） A and ,8 = 91.660（3）°. For 1, five CN groups of Fe（CN）6]4- are involved in bridging. The polymer displays a 3D open microporous framework with 5-connected uninodal （46.64） topology.

Synthesis and Characterization of Heterobimetallic Zigzag Chains with a Close-packed Structure Based on Macrocyclic Metalloligands

Two new heterobimetallic coordination polymers{[Co(NiL)(H2O)3]·4H2O}n(1)and{[Cu(NiL)(H2O)3]·4H2O}n(2)were synthesized based on metalloligand under the same self-assembly conditions.X-ray diffraction analyses reveal that the two compounds involve close-packed zigzag chains,which expand into various three-dimensional supramolecular frameworks through the second interactions such as hydrogen bonds andπ···πstacking interactions.In these two compounds,NiL as a bridging ligand chelates the metal ion nodes via two oxamido carbonyls and carboxylate oxygen atom.The central Co(Ⅱ)and Cu(Ⅱ)ions in 1 and 2 both exhibit distorted octahedral coordination geometry.They are bridged by macrocyclic oxamido metalloligands fusing the zigzag chains with a‘‘head-to-tail’’arrangement.The Ni(Ⅱ)ion in metalloligand is coordinated by four nitrogen atoms with the[NiN4]chromophore exhibiting distorted planarity.The two investigated compounds were further characterized by thermogravimetric analysis and FT-IR spectroscopy.The fluorescent properties of 1 and 2 in the solid state were also investigated.

N,N,O-Tridentate One-dimensional Methyl-bridged Heterobimetallic Complex: Synthesis, Crystal Structure and Catalytic Activity

The sequential reaction of the N,N,O-tridentate ligand HOC(CH2)5CH2N(Me)CH2CH2NMe2(LH)in diethyl ether with AlEtCl2 and MeLi afforded a lithium-aluminum complex containing a polymeric structure of one-dimensional chain[{-LiOC(CH2)5CH2N(Me)CH2CH2NMe2}AlMe2CH3-}n](1),which was characterized by 1H,13C NMR spectra,elemental analyses and single-crystal X-ray diffraction analysis.Complex 1 crystallizes in triclinic,space group P1 with a=10.526(3),b=10.949(3),c=17.799(4)?,β=76.211(11)°,V=1915.3(8)?3,Dc=1.014 g·cm–3,F(000)=648 andμ=0.104 mm–1.In addition,the heterobimetallic complex 1 was used to catalyze the Meerwein-Ponndorf-Verley(MPV)reaction and exhibited excellent catalytic activities in good yield(up to 97%).

Heterobimetallic complexes CpNiCo(CO)_2(PPh_3)(PhC_2C_6H_4-R-p): their synthesis, electrochemistry and ESR

Three new heterobimetallic acetylene complexes CpNiCo （CO）（PPh） （PhCCH-R-p） [R =H（2）, Br（3）, COCH（4）] have been synthesized in suitable yield （31-47％） via the reaction of（PhCCH-R-p）CO（CO）PPhwith nickelcene in n-octane. The complex CpNiCo（CO）（PhC） （1）has also been obtained in 12％ by the reaction of （PhC） Co（CO）with nickelcene. The complexeshave been characterized by elemental analysis, IR andH NMR. Electrochemical study of redoxcouples of these complexes was presented by using cyclic voltammetry on Pt electrodes in acetone.At room temperature, all complexes underwent electrochemically reversible or guasi-reversible one-electron oxidation or reduction to the stable radicals. The radical anions of the complexes couldbe easily detected by ESR method in situ electrolysis in the THF solution. The isotropic parameters,Co= 2.20mT, <g> = 2.052 for the radical anion of complex 1, Co= 2.20 mT, p = 1.42 mT,

Synthesis and Crystal Structure of a Novel Hexanuclear Copper-indium Thiolate Complex [(InCl)_2(OMe)(μ-OMe)_2(μ_3-OMe)(μ-SPr^n)_2(CuPPh_3)]_2

A novel hexanuclear copper-indium thiolate complex, [（InCl）2（OMe）（μ-OMe）2（μ- OMe）（μ-SPrn）2（CuPPh3）]2 1, was synthesized from the reaction of NaSPrn, InCl3 and [Cu（Me- CN）a][PF6] in the presence of Ph3P and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P211n with a = 11.3533（8）, b = 15.4939（11）, c = 20.5189（14） A, β = 98.577（2）°, V = 3569.0（4） A3, Z = 2, C56H82Cl4Cu2In4O8P2S4, Mr = 1801.56, Dc = 1.676 g/cm3,μ（MoKa） = 2.213 mm^-1, F（000） = 1796, S = 0.985, the final R = 0.0559 and wR = 0.1099 for 8878 observed reflections with I 〉 2σ（I） and 367 variables. Complex 1 consists of two CuPPh3 fragments which symmetrically side-attach to the tetranuclear core of [InaCl4（OMe）2（μ-OMe）a（μ- OMe）2（μ-SPrn）4] by coordinating with sulfur atoms of propane-thio moieties. The average In-Ot （terminal）, In-μ-O and In-μ3-O bond distances are 2.305（4）, 2.144（4） and 2.294（4） A, respectively.

Synthesis, structure and catalytic behavior of ytterbium complexes bearing a phenoxy(quinolinyl)amide ligand

Two ytterbium complexes stabilized by phenoxy（quinolinyl）amide ligand 3,5-But2-2-OC6H2CH2N-8-C9H6N （L） were synthesized and characterized. Reaction of anhydrous YbC13 with 1 equiv, of LLi2 in THF gave the ytterbium chloride [LYbCI（THF）]2 （1） in 73% yield. A further reaction of complex 1 with equimolar of NaN（SiMe3）2 in THF afforded the unexpected heterobimetallic ＂ate＂-complex L2YbNa（THF）2 （2） via a ligand redistribution reaction. Complex 2 could also be prepared in high isolated yield by the reaction of anhydrous YbC13 with 2 equiv, of LNa2 generated in situ. Both complexes 1 and 2 were characterized by IR spectroscopy, elemental analysis, and sin- gle-crystal X-ray diffraction analysis. It was found that complex 2 was an effective catalyst for the addition reaction of aromatic amines to carbodiimides.

Haptotropic Migration of Metal Templates on Arene Surfaces

1 Results The chromium-templated benzannulation of arylcarbenes by alkynes provides a direct regio- and diastereoselective access to densely functionalized chromium arenes[1]. The chromium fragment undergoes a haptotropic migration along the π-face of the fused arenes which can be controlled by thermodynamics,by the substitution pattern of the arene and by the metal coligand sphere(See Scheme 1).The controlled regioselective labeling of benzene rings can be exploited in diastereoselective C-C bond forma...

Heterometal–organic frameworks: Three novel copper(Ⅱ)–lanthanide(Ⅲ) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platform

Reactions of copper（Ⅱ） sulfate or copper（Ⅱ） perchlorate,samarium（Ⅲ）,erbium（Ⅲ） or neodymium（Ⅲ）nitrate（5/1 equiv.） with pyrazinohydroxamic acid（H2Pyzha） in H2O/Me0 H led to three new heterobimetallic 15-metallacrown-5 complexes.In a MeOH/H2O solution,when adding inorganic salts,the ligands exist as protonated metallacrowns.In the solid state,their structures are more complicated as confirmed by X-ray analysis：metallacrown[Sm（H2O）3 {Cu（pyzha）}5（H2O）2（MeOH）（HSO4）2]·（H2O）2（HSO4）（1）;[Nd（H2O）2（MeOH） {Cu（pyzha）}5（ClO4）2（H2O）5（NO3）]（2）;[Eu（H2O）2（MeOH） {Cu（pyzha）}5（ClO4）2（H2O）5（NO3）]（3）.The differentiation of atomic and ionic radii between the encapsulated lanthanide（Ⅲ） could be used to control the bowl-shape distortion of the metallacrowns from the planar geometry.The complex 1 clearly exhibits fluorescence behavior of samarium（Ⅲ）,while 2and 3 show that of copper（Ⅱ） and ligand.

Synthesis,characterization and magnetism of copper(Ⅱ)-lan-thanide(Ⅲ) heterobimetalic complexes with N,N'-oxamidobis-(benzoato) cuprate (Ⅱ)

Seven new μ-oxamido copper(Ⅱ)-lanthanide(Ⅲ)hetero-bitnetalic complexes described by the fonnula Cu(obbz)Ln-(Ph-phen)2NO3(Ln=La,Nd,Eu,Gd,Tb,Ho,Er),where obbz denotes the oxamidobis(benzoato)and Ph-phen represents 5-phenyl-1,10-phenanthroline,have been synthesized and characterized by the elemental analyses,spectro-scopic(IR,UV,ESR)studies,magnetic moments(at room temperature)and molar conductivity measurement.The temperature dependence of the magnetic susceptibility of Cu(obbz)Gd(Ph-phen)2NO3 complex has been measured over the range 4.2-300 K.The least-squares fit of the experimental susceptibilities based on the spin Hamiltonian operator,H=-2JS1 S2,yielded J=+1.28 cm-1,a weak ferromagnetic coupling.A plausible mechanism for a ferromagnetic coupling between Gd(Ⅲ)-Cu(Ⅱ)is discussed in terms of spin-polarization.