配合物(ArO)2Yb(NPh2)2K(THF)4(Ar=C6H2-t-Bu3-2,4,6)的合成、分子结构和催化行为

Reaction of anhydrous YbC13 with 2 equiv, of sodium 2,4,6-tri-tert-butylphenoxide (ArONa, Ar=C6H2-t-Bu3-2,4,6) and 2 equiv, of potassium diphenyl amide in THF afforded the first bis(aryloxo) amido-lanthanide complex of (ArO)2Yb(NPh2)2K(THF)4 (1). In 1, the ytterbium and potassium were bridged via diphenyl amido ligands.The ytterbium metal center was coordinated to two oxygen atoms of aryloxide ligands and two nitrogen atoms of diphenyl amido ligands in a conventional distorted tetrahedral fashion, while the potassium interacted in η^2-fashion with two phenyl rings of the diphenyl amido ligands besides four THF molecules. 1 displayed moderate catalytic activities for the polymerization of methyl methacrylate and acrylonitrile.     

Syntheses and Characterization of Half—Sandwich Zirconium Complexes with Dichalcogenolate o—Carborane Ligands

Metallocene complex Cp2^ttZrCl2(Cp^tt=η^5-1,3-^tBu2C5H3)(1)has been prepared from the reaction of LiCp^tt with ZrCl4 in good yield.Reactions of 1 with dilithium dichalcogenolate o-carboranes afforded new type of half-sandwich compounds with dichalcogenolate o-carboranyl ligands,[Li(THF)4][Cp^ttZr(E2C2B10H10)2](E=S,2a;E=Se,2b)in which only one cyclopentadienyl ring ligand existed.Complexes 1 and 2a were structurally characterized by X-ray analyses.In complex 2a,the Zr(IV)ion is η^5-bound to one 1,3-ditert-cyclopentadienyl ring and σ-bound to four μ2-sulfur atoms of two dithio-carboranes.the zirconium atom and four sulfur atoms form a distorted pyramid.The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur stoms and the fulcrum at the zirconium stom.     

Synthesis, Crystal Structure and Characterization of α-（1-Benzimidazolyl） -hypnone Cobalt（Ⅱ） Complex： [CoCl （ C7H5N2CH2COPh）4] Br

The crystal structure of [CoCl ( C7H5N2CH2COPh)4] Br has been determined by means of X-ray crystallography. The molecular structure consists of a discrete [CoCl ( C7H5N2CH2COPh)4] ^ cation and one Br^- anion, in the [CoCl ( C7H5N2CH2COPh)4]^ cation, the coordination geometry of the central Co atom is square-pyramidal with four tertiary N atoms of benzimidazole from four α-( benzimidazol-1-yl) -hypnone ligands in the basal position and one chloride anion in the apical position. In the solid state, [CoCl ( C7H5N2CH2COPh)4]^ and Br^- anion possess intermolecular and intramolecular interactions, which stabilize the crystal structure. The characterization of the title compound were also carried out by using elemeutal analysis, FTIR, UV spectrometries and TG-DSC.     

Syntheses and Crystal Structures of （PySe）2 and Bi2（PySe）6（HPySe=2-Pyridineselenol N-Oxide）

The title compounds(PySe)2 1(HPySe=2-pyridineselenol N-oxide,(PySe)2= bis(2-pyridine-N-oxide) diselenide) and Bi2(PySe)6 2 were prepared by the reaction of 2-bromine-N-oxide with NaHSe and Bi(NO3)3·5H2O with HPySe,and the crystal structure of 2 was studied.Compound 2 crystallizes in the monoclinic space group P21/n with a=9.840(2),b=10.204(2),c=18.395(2),β=102.926(2)°,V=1800.0(5)3,Dc=2.2687 g/cm3,Z=2,the final R=0.0319 and wR=0.0646.The Bi atoms are coordinated by four selenium and four oxygen atoms from four PySe ligands to form a slightly distorted four-column geometry.     

A Novel Two-dimensional Lead(Ⅱ) Coordination Polymer Based on Dinuclear Lead(Ⅱ) Unit Containing(5-Chloro-quinolin-8-yloxy) Acetate

A novel two-dimensional lead(II) coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand(5-chloro-quinolin-8-yloxy)acetic acid(HL) with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603(7), b = 8.6907(4), c = 8.4745(3), β = 101.1110(11)°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25(9)3, Z = 4, Dc = 2.628 g/cm3, F(000) = 880, μ = 14.367 mm-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead(II) cation, one(5-chloro-quinolin-8-yloxy)acetate(L) ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit(SBU) and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H···Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079(1). The fluorescence emission peak of complex 1 appears near 407 nm.     

Synthesis and Crystal Structure of an Unusual Dodecacoordinated Lanthanum Complex by Phenanthroline and Nitrate （phenH）_2[La（NO_3）_5（phen）]·CH_3OH

Lanthanum complex (phenH)2[La(NO3)5(phen)]·CH3OH (1, phen=phenanthroline) was synthesized and characterized by single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a=20.3040(3), b=10.7091(1), c=19.0771(2), β=102.090(1)°, V=4056.07(8)3, Z=4, Dc=1.676 g/cm3, μ= 1.142 mm-1, F(000)=2056, the final R=0.0346 and wR=0.0793 for 9981 (Rint=0.0358) independent reflections. The mononuclear complex 1 consists of four parts: two phenH+ cations formed by the protonation of phen, one complex anion [La(NO3)5(phen)]2-, and one solvent methanol molecule. The complex anion contains one phen and five nitrate ligands which both chelate the center La(III) ion, adopting a distorted twelve-coordinated icosahedral geometry. The cations, anion and solvent molecule are linked together by hydrogen bonds. One of the protonated phenanthrolines (phenH+) acting as cation connects to the anion via N–H…O hydrogen bond directly, and the other one links to the anion through an intermediate solvent CH3OH via N–H…O and O–H…O hydrogen bonds. By the plentiful additional weak C–H…O intermolecular hydrogen bonds, the compound molecules construct a two-dimensional layer 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 and Crystal Structure of a 1-D Chain Zinc（Ⅱ） Coordinated Polymer with N-p-Tolysulfonyl-glutamine

A novel coordination polymer {[Zn(ts-gln)(bipy)]3H2O}n (ts-glnH2=N-p-toly-sulfonyl-glutamine,bipy=2,2-bipyridine) has been prepared and structurally characterized by X-ray diffraction method. It crystallizes in orthorhombic,space group P212121 with a=8.2622(5),b=16.6244(10),c=18.2807(10) ,V=2510.9(3) 3,C22H28N4O8SZn,Mr=573.91,Z=4,Dc= 1.518 g/cm3,μ(MoKa)=1.115 mm-1,F(000)=1192,the final R=0.0262 and wR=0.0662 for 5691 independent reflections with Rint=0.0240. The zinc(Ⅱ) atom is coordinated by N(3) and N(4) atoms of a bipy molecule,two carboxylate O(1) and O(2A) and amino N(1) atoms of ts-gln ligands,resulting in a square-pyramidal geometry. The title complex consists of an infinite zigzag chain of zinc(Ⅱ) ions linked by the carboxylate of N-p-tolysulfonyl-glutamine.     

Unexpected Synthesis and Crystal Structure of Macrocyclic Nickel Complex Involving Rare S-Cl Bond

A novel complex of [NiL(OOCNH2C2H3SClO3)]·H2O was obtained unexpectedly by the reaction of [Ni(rac-L)](ClO4)2 with l-cysteine (L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra- azacyclotetradecane), and characterized by EA, IR, ESI-MS and single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group P212121 with a=9.211(12), b=14.942(19), c=19.002(2), Mr=563.80, V=2615.3(6)3 , Z=4, Dc=1.432 g/cm3 , F(000)=1204, μ=0.966 mm-1 , the final R=0.0565 and wR=0.1515. The central nickel(Ⅱ) ion displays a distorted six-coordinate octahedral coordination geometry by coordination with four nitrogen atoms of L, and one oxygen and one nitrogen atoms of l-cysteine. The sulfur atom of l-cysteine instead of oxygen atom links directly with the chlorine atom of perchlorate. The title complex is the first example of perchlorate salt involving the sulfur atom.     

Synthesis and Crystal Structure of a Novel 1D Magnesium （Ⅱ） Coordination Polymer Constructed by L-Cysteic Acid

A novel coordination polymer [Mg(L)(H2O)2]·H2O] (LH2=L-cysteic acid) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction.The crystal crystallizes in orthorhombic system, space group P212121, with a=5.962(3), b=11.224(6), c=13.664(7)(A), V=914.3(8) (A)3, Z=4, Mr=245.50, Dc=1.783 g/cm3,μ=0.445 mm-1,flack parameter=0.32(16), F(000)=512, the final R=0.0458 and wR=0.1172 for 1578 observed reflections with I ＞ 2σ(Ⅰ). The Mg(Ⅱ) atom shows an octahedral geometry defined by two carboxyl O atoms from two different L-cysteic acid ligands, one carboxyl O atom and one amino N atom from the adjacent ligand, and two aqua ligands. The Mg(Ⅱ) atoms are bridged by L-cysteic acid ligands, leading to a 1D infinite zigzag chain. In the structure there are extensive hydrogen bonds,through which the complex completes its 3D framework structure.     

Synthesis and Crystal Structure of a New [Mn_2Ni_2] Cubane Complex

A new Mn2Ni2 cubane complex has been synthesized and characterized by single-crystal X-ray diffraction,FT IR spectra and elemental analysis.The title compound [MnIII2NiII2(hmp)4(N3)4(O2CR)2](hmp-is the anion of 2-pyridinemethanol and O2CR-is α-na-phthaleneacetate)crystallizes in the monoclinic system,space group P21/c with a = 10.519(5),b = 22.109(10),c = 23.235(9),β = 106.096(17)o,C48H42Mn2N16Ni2O8,Mr = 1198.28,V = 5192(4)3,Dc = 1.533 g/cm3,F(000)= 2448,μ = 1.258 cm1,Z = 4,the final R = 0.0875 and wR = 0.2020 for 3398 reflections with I > 2σ(I).X-ray diffraction analysis reveals that each Mn(III)center is octahedrally coordinated by two nitrogen atoms of azide anions and three oxygen atoms from three 2-pyridinemethanol anion ligands together with one oxygen atom from naphthaleneacetate.Each Ni(II)is octahedrally coordinated by two nitrogen atoms of 2-pyridinemethanol anion ligands as well as three oxygen atoms from three 2-pyridinemethanol anion ligands and one oxygen atom from naphthaleneacetate.     

Synthesis and Crystal Structure of Diaquabis{2,4-dibromo-6-[(2-ethylaminoethylimino)methyl]-phenolato}nickel(Ⅱ) Dinitrate Diacetonitrile

The title mononuclear Schiff base nickel(Ⅱ) complex [Ni(C11H14Br2N2O)2(H2O)2]· 2NO3·2C2H3N was prepared and characterized by elemental analysis,IR spectrum,and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system,space group P21/n with a=15.534(2),b=7.647(1),c=16.435(2),β=103.252(2)o,V=1900.3(4)3,Z=2,Dc=1.750 g/cm3,Mr=1000.99,λ(MoKα)=0.71073,μ=4.776 mm-1,F(000)=996,the final R=0.0368 and wR=0.0724. A total of 3988 unique reflections were collected,of which 2764 with I > 2σ(I) were observed. The complex consists of a mononuclear [Ni(C11H14Br2N2O)2(H2O)2]2+ cation,two nitrate anions and two acetonitrile molecules. The Ni atom,lying on the inversion centre,is six-coordinated by two Schiff bases and two water molecules to assume an octahedral coordination geometry. The molecules in the crystal are linked through intermolecular hydrogen bonds of N–H…O,N–H…Br,O–H…O,O–H…N and C–H…O to form layers.     

Diverse heteroleptic ytterbium(III) thiocyanate complexes by oxidation from bis(thiocyanato)ytterbium(II)

The new ytterbium(II) thiocyanate complex [Yb(NCS)2(thf)2] (1), synthesised by redox transmetallation between [Hg(SCN)2] and ytterbium metal in THF at room temperature, gave monomeric, eight coordinate [Yb-(NCS)2(dme)3] (2, dme = 1,2-dimethoxyethane) on crystallisation from DME, and is a powerful, synthetically useful reductant. Thus, oxidation of 1 with Hg(SCN)2, Hg(C6F5)2/HOdpp (HOdpp = 2,6-diphenylphenol), TlCp (Cp = C5H5 or CH3C5H4), Tl(Ph2pz) (Ph2pz = 3,5-diphenylpyrazolate) and CCl3CCl3 in THF yielded the ytterbium(II) complexes [Yb(NCS)3(thf)4] (3), [Yb-(NCS)2(Odpp)(thf)3](4), [Yb(NCS)2Cp-(thf)3] (Cp = C5H5 (5), CH3C5H4 (6)), [Yb(NCS)2(Ph2pz)(thf)4] (7) and [Yb(NCS)2Cl(thf)4] (8). In the solid state, complexes 4, 6 and 7 were shown by X-ray crystallography to be six, eight and eight coordinate monomers, respectively. Exclusively terminal, N-bound transoid thiocyanate bonding is observed with eta1-Odpp (4), eta5/-C5H4Me (6) and eta2-Ph2Pz (7) ligands attached approximately perpendicular to the N...N vector. The chloride complex 8 is not a molecular species, but consists of discrete, seven coordinate [YbCl2(thf)5] cations and [Yb(NCS)4(thf)3] anions. By contrast, oxidation of 1 with TlO2CPh gave a mixture of [[Yb(NCS)-(O2CPh)2(thf)2]2] (9) and 3 through rearrangement of an initially formed [Yb(NCS)2(O2CPh)] species. The X-ray structure of 9 indicates a dimeric complex with a (Yb(mu-O2CPh)4Yb] core that contains both bridging bidentate and bridging tridentate benzoate groups, and with a terminal N-bound thiocyanate and two THF ligands on each ytterbium. Reduction of Ph2CO with 1 in THF yielded the dinuclear complex [[Yb(NCS)2(thf)3]2(mu-OC(Ph)2C(Ph)2O)] (10), in which two octahedral Yb centres are bridged by a 1,1,2,2-tetraphenylethane-1,2-diolate ligand, derived from reductive coupling of the benzophenone reagent.     

Synthesis and Crystal Structure of Bis(cyclopentadienyl) Ytterbium Complex Supported by β-Diketiminate

Treatment of the β-diketiminate-supported ytterbium dichloride LYbCl2(THF)2 1 (L = N,N'-bis(2,6-dimethylphenyl)-2,4-pentanediiminate) with 2 equiv of C5H5Na gave rise to the title complex LYb(C5H5)2 2 (C31H35N2Yb, Mr = 608.65), and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 14.417(2), b = 10.432(2), c = 18.040(4)(A),β= 95.73(2)°, V = 2699.6(9)(A)3, Dc = 1.498 g/cm3, Z = 4,λ(MoKα) = 0.71073(A), μ = 3.485 mm(1, F(000) = 1220, the final R = 0.0304 and wR = 0.0703 for 3962 observed reflections with I > 2σ(I). In the molecular structure of the title complex, the central metal atom Yb is eight-coordinated by two cyclopentadienyl groups and two nitrogen atoms of β- diketiminate group to form a distorted tetrahedral geometry.     

金属配位聚合物[Mn2（C8H3NO6）2(C12H8N2)2]n的合成及其催化氧化性能

以5-硝基间苯二甲酸,1,10-邻菲啰啉,硫酸锰(MnSO4.H2O)为原料合成了一种结构新颖的金属配位聚合物——[Mn2(C8H3NO6)2(C12H8N2)2]n(1),其结构经IR,XRD,TG-DTG和元素分析表征。X-射线单晶衍射测试结果表明,1属三斜晶系,空间群Pī,晶胞参数a=10.060 2(1),b=14.343 5(2),c=14.663 7(2),α=104.052(1)°,β=102.633(1)°,γ=110.460(1)°,Mr=888.52,V=1 812.69(4)3,Z=2,Dc=1.628 g.cm-3,F(000)=900。以30%H2O2为氧化剂,初步研究了1在苯乙烯氧化反应中的催化氧化性能。     

Crystal Structure of[PrAl(CF3COO)2(CF3CHOO)(C2H5)2(C4H8O)2]2

[PrAl(CF3COO)2(CF3CHOO)(C2H5)2(C4H8O)2]2 Mr=1420.56, monoclinic, P21/n, a=10.651(6), b=24.276(9), c=11.110(5)(), β=107.650(4)°, V=2737.4(1)()3, Z=2, Dc=3.45 g/cm3, F(000)=2816, T=233K, MoKα radiation (λ=0.71069()), μ(MoKα)=38.017 cm-1, R=0.048 for 2847 observed reflections (I≥3σ(I)). It is isostructural with [LnAl(CF3COO)2(CF3CHOO)-R2(C4H8O)2]2 (Ln=Ho, R=Et; Ln=Nd, Y, R=iBu). Pr3+ is coordinated by eight oxygen atoms from five bridging ligands and two THF forming a distorted bicap-prism.     

Synthesis and Crystal Structure of Tetra（diisopropylamido—N）ytterbium Mono（tetrahydrofuran—O）lithium

1 INTRODUCTION The lanthanide amide complexes are excellent synthetic precursors for lanthanide derivatives, par- ticularly in the reactions involving protonic rea- gents[1]. A few types of lanthanide amide complexes, from homoleptic three- to four-coordinate, have been known for some time[2～4]. Recently, we begin to examine the utility of amide with less steric bulk, such as diphenylamide and diisopropyamide, as li- gands to synthesize homoleptic lanthanide amide complexes. For diphen…     

Synthesis,Crystal Structure and Luminescent Property of a New Copper(Ⅰ) Iodide Complex Based on 3,5-Dimethyl-4-amino-triazole

The title compound,[Cu4I4(C4H8N4)4],has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in monoclinic,space group Pbca,with a=18.1851(10),b=9.3697(5),c=19.8034(10),V=3374.3(3)3,C16H32Cu4I4N16,Mr=1210.34,Z=4,Dc=2.383 g/cm3,μ=6.183 mm-1,F(000)=2272,S=1.032,the final R=0.0309 and wR=0.1180 for 3854 observer reflections(I2σ(I)).The structure of the title compound consists of tetranuclear copper cluster units bridged by the halogen atoms with the 3,5-dimethyl-4-aminotriazole ligands coordinated to the metal ions through the triazole nitrogen atoms.The luminescent property of 1 was also studied.     

Synthesis and Crystal Structure of a New Complex [Cd（C20H14N4）2Cl2]

The title compound [Cd(C20H14N4)2Cl2] 1 was synthesized via the hydrothermal reaction of CdCl2·7H2O and NaOH with 1,3-bis(benzimidazol-2-yl)benzene (BMB), and characterized by elemental analysis and infrared spectra. The crystal of 1 crystallizes in monoclinic, space group C2/c with a = 21.021(6), b = 9.489(3), c = 18.302(6), β = 108.686(6)o, V = 3458.2(19)3, Z = 4, C40H28CdN8Cl2, Mr = 804.01, Dc = 1.544 g/cm3, F(000) = 1624 and μ(MoKα) = 0.829 mm-1. The final R = 0.0306 and wR = 0.0779 for 3334 observed reflections with I > 2σ(I) and R = 0.0796 and wR = 0.0360 for all data. The cadmium atom is four-coordinated by the BMB ligands and Cl atom with a tetrahedral geometry. The extensive N-H···N hydrogen bonding interactions are observed in the structure, which further extend the [Cd(C20H14N4)2Cl2] units into a 1D structure. The thermogravimetric analysis measurement showed that compound 1 has thermal stability as no strictly clean weight loss step occurred below 425 ℃.     

Synthesis and Structure of a Novel Cobalt(Ⅱ)Complex with the Tertiary Carbinol Derivative of Di-4-pyridinylmethanone

The title complex [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞ was obtained and characterized through elemental analysis, FT-IR and X-ray crystallography. The complex crystallizes in space group P3(2)21 with a=10.2480(11), b=10.2480(11), c=26.943(6), β=120.00°, [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞, C28H34CoN8O8 , Mr=669.56, Z=3, V=2450.5(7)3 , Dc=1.361 g·cm-3 , μ=0.584 mm-1 , F(000)=1047, R=0.0498 and wR=0.1301. The Co(Ⅱ) center exhibits a N4O2-octahedral coordination geometry surrounded by a pair of nitrates at the axial positions and four pyridyl N atoms at the equatorial sites. An infinite double-bridged chain structure with μ2-bridging (4-C5H4N)2C(OH)(NHC3H7) ligands is formed, which is the in situ product of metal-promoted nucleophilic addition reaction of propan-1-amine with di-4-pyridinylmethanone ((4-C5H4N)2CO) in the presence of Co(NO3)2·6H2O. It is the first tertiary carbinol metal complex derived from di-4-pyridinylmethanone so far, and also the rare example of tertiary carbinol derivative of dipyridylmethanone family. The nucleophilic reaction at the carbonyl of dipyridylmethanone in the presence of metal salt will be discussed.