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.

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.