Syntheses, characterization and ethylene polymerization of half-sandwich group IV metal complexes with tridentate [O,N,S] ligands

A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O NS] ligand [2-Bu t 4-Me-6-((2-(SC 6 H 5)C 6 H 4 N = CHC 6 H 2 O)](La) and dianionic phenoxy-amine arylsulfide [O N S] ligand [2-Bu t 4-Me-6-((2-(SC 6 H 5)C 6 H 4 N-CH 2 C 6 H 2 O)] 2(Lb) have been synthesized and characterized.Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH 4 in cool diethyl ether.Half-sandwich Group IV metal complexes CpTi[O NS]Cl 2(1a),CpZr[O NS]Cl 2(1b),CpTi[O N S]Cl(2a),CpZr[O N S]Cl(2b) and Cp * Zr[O N S]Cl(2c) were synthesized by the reactions of La and Lb with CpTiCl 3,CpZrCl 3 and Cp * ZrCl 3,and characterized by IR,1 H-NMR,13 C-NMR and elemental analysis.In addition,an X-ray structure analysis was performed on ligand Lb.The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane(MAO) as co-catalyst up to 1.58 × 10 7 g-PE.mol-Zr 1.h 1.The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.     

Synthesis and Crystal Structure of [CpRu（η^5-C5H5）（dppc）Cl][PF6]

1INTRODUCTION The fragment[Ru(η5-C5H5)(PPh3)2Cl]plays an important role in the organo-ruthenium chemistry development,and has been used as a versatile star-ting material for other compounds due to its stability and facile manipulation.Much work has shown that a wide range of ligands with different steric and electronic properties can displace not only the Cl ligand but also the phosphine groups in[Ru(η5-C5H5)(PPh3)2Cl][1].The interest in this fragment and related derivatives concer…     

Preparation and Characterization of A New Dinuclear Ruthenium Complex with BDPX Ligand and Its Catalytic Hydrogenation Reactions for Cinnamaldehyde

Introduction Recently, dinuclear Ru complexes containing chelating bidentate phosphines (either chiral or non-chiral) have attracted more and more attention owing to their effective ability for catalytic hydrogenation of olefins and carbonyl groups under mild conditions. A great number of dinuclear Ru complexes with bidentate phosphines have been obtained.1-10 In 1985 Ikariya et al.1 prepared a chiral binuclear ruthenium complex [Ru2Cl4(BINAP)2]NEt3 by the reaction of (S)-BINAP with [R…     

Hydrothermal Syntheses,Crystal Structures,TGA and Electrochemistry Properties of Two Metal-organic Coordination Compounds Based on 4'-((1H-1,2,4-triazol-1-yl)methyl)-[1,1'-biphenyl]-2-carbonitril

Two novel metal-organic coordination compounds with molecular structures of {[Co(TMBC)4Cl2]·2H2O}(1) and {[Ni(TMBC)4Cl2]·2H2O}(2)(TMBC = 4'-((1H-1,2,4-triazol-1-yl)methyl)-[1,1'-biphenyl]-2-carbonitrile), have been synthesized under hydrothermal conditions of Co Cl2·6H2O and Ni Cl2·6H2O with 4'-((1H-1,2,4-triazol-1-yl)methyl)-[1,1'-biphenyl]-2-carbonitrile, respectively. Both compounds crystallize in triclinic systems, space group P 1. They are characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectroscopy and TGA. Moreover, their electrochemical behaviors have also been studied in different electrolyte solutions, respectively.     

含硫有机膦多酸衍生物α–[RP(S)]2PW9O345-(R = –C6H5, –C6H11)的合成及结构表征

In the presence of Bu4NBr acting as phasetransfer reagent, organothiophosphoryl polyoxotungstate derivatives α-[RP(S)]2PW9O54^5- (R=C6Hs, C6H11) have been obtained by reaction of the trivacant β-[PW9O34]^9- anions with electrophilic C6H5P(S)Cl2 or C6H11P(S)Cl2 in acetonitrile. These new organic-inorganic hybrid anions have been characterized by elemental analysis, IR, ^31P and ^183W NMR spectroscopy. The collective application of the spectroscopy data of these new species indicates that the hybrid anion consists of an α-[PW9O34] framework on which are grafted two RP(S) groups through P-O-W bridges. The five-line ^183W spectra indicate that the hybrid anions possess Cs symmetry in acetonitrile.     

Synthesis,Structure and Catalytic Activity of a Manganese(Ⅲ) Complex Based on 2-(2-Hydroxyphenyl)-5,6-dichlorobenzimidazole Ligands

A new ligand, 2-(2-hydroxyphenyl)-5,6-dichlorobenzimidazole, H2pbmCl2(1), and a novel MnIII complex, [MnIII(HpbmCl2)(pbmCl2)(DMF)2](2),(DMF = N,N-dimethylformamide), have been synthesized and characterized. The crystal of compound 1(C13H8Cl2N2O, Mr = 279.12) belongs to the monoclinic system, space group P21 with a = 3.770(5), b = 25.20(3), c = 5.865(7) , = 92.727(17)o, V = 556.6(12) 3, Z = 2, Dc = 1.665 g/cm3, S = 1.137, μ= 0.568 mm-1, F(000) = 284, the final R = 0.0876 and wR = 0.2334 for 1848 independent reflections. The molecule is planar due to the presence of a strong intramolecular hydrogen bond between O–H group of phenol and N atom of imidazole. H2pbmCl2(1) molecules are arranged into a one-dimensional linear chain through intermolecular hydrogen bonds(N–H···O and C–H···Cl). The crystal of complex 2(C32H27Cl4MnN6O4, Mr = 756.34) belongs to the monoclinic system, space group P21/c with a = 19.043(10), b = 10.808(5), c = 18.704(11), = 115.540(6)o, V = 3473(3) 3, Z = 4, Dc = 1.446 g/cm3, S = 1.3, μ = 0.733 mm-1, F(000) = 1544, the final R = 0.1219 and wR = 0.2681 for 7811 independent reflections. The Mn ion adopts a distorted octahedral geometry coordinated by two deprotonated H2pbmCl2 ligands and two DMF molecules. The [MnIII(HpbmCl2)(pbmCl2)(DMF)2] molecules are arranged into a three-dimensional structure through hydrogen bonds(N–H···N, C–H···N and C–H···Cl) and weak π···πinteractions. The activity measurements suggest that complex 2 is able to serve as a catalyst for H2O2 disproportionation reaction to form O2 in neutral water solution.     

^31P NMR Studies on the Ligand Dissociation of Trinuclear Molybde-num Cluster Compounds

A series of carboxylate-substituted trinudear molybdenum dus-ter compounds formulated as Mo3S4(DTP)3(RCO2)(L), where RffiH, CH3, C2H5, CH2Cl, CCl3, R^1C6H4(R^1 is the group on the benzene ring of aromatic carboxylate ), L=pyridine,CH3CN, DMF, have been synthesized by the ligand substitu-tion reaction. The dissociation of the loosely-coordinated ligand L from the cluster core was studied by ^31p NMR. The dissocia-tion process of L is related to the solvent, temperature, and acidity of carboxylate groups, so as to affect the solution struc-ture and reactive properties of the duster. The long-distance in-teraction between ligands RCO2 and L is transported by Mo3S4 core.     

Effect of pH/Auxiliary Ligand on the Structures of Coordination Compounds Based on a Novel Ligand 2,6-Bis(pyrazin-2-yl)pyridine-4-carboxylate

Four new coordination compounds, [Zn(bppc)_2(H_2O)_2]·3 H_2O(1), [Zn2(bppc)2(mbdc)(H_2O)4]·7 H_2O(2), [Zn(bppc)2(H_2O)2]n·n(m-Hbdc)·n(H_2O)(3), [Zn2(bppc)(btc)(H_2O)3]n·5 n H_2O(4)(Hbppc = 2,6-bis(pyrazin-2-yl)pyridine-4-carboxylate, H2(m-bdc) = 1,3-benzenedicarboxylic acid, H3 btc = 1,3,5-benzene-tricarboxylic acid), have been hydrothermally synthesized and structurally characterized. Compound 1 shows a mononuclear structure and 2 shows a dinuclear structure. Compound 3 is a one-dimensional chain structure, which is extended into a 3D supramolecular network by intermolecular hydrogen interactions. In 4, a 1D loop-like chain is connected by(btc)3-anions to generate a 2D layer structure. The structure differences of 1~4 show that the p H and aromatic acid as auxiliary ligand have important influence on the final structures.iAdditionally, the luminescent properties of 1~4 have been investigated with fluorescent spectra in the solid state, and 1~4 display a strong fluorescent emission at room temperature and have potential applications as fluorescent-emitting materials.     

Synthesis and Crystal Structure of {(PPh3)2ClRu(μ-Cl)-Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O)

The title compound has been synthesized by the reaction of [RuCl2(PPh3)3] and closo-[B10H10]2- in (CH3)2CHOH solution. Crystals suitable for a single crystal X-ray diffraction analysis were obtained from n-pentane diffused to CH2Cl2 solution. The crystal {(PPh3)2ClRu(μ-Cl)Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O) is monoclinic , space group P21/n , Mr=1359.47, with a=19.434(4), b =14.340(4), c=25.865(9)(A), β= 95.48(3)°, V=7175(4)(A)3, Dc=1.258 g/cm3, Z=4, λ(MoKα)=0.71073(A),μ=6.03 cm-1, F(000)=2784, R=0.0631, wR2= 0.1425, S=1.001. The title compound is a bimetallic species in which the second ruthenium center is bound to the cluster {(PPh3)RuB10H7[OCH(CH3)2]3} via an Ru-Cl-Ru and two Ru-H-B-Ru bridges. The third isoproxy group replaces a hydrogen atom on B(10) of the cage, which indicates the activity of the cage.     

EFFECTS OF K_2O AND MnO PROMOTERS ON THE PRODUCTION OF LIGHT ALKENES VIA SYNGAS OVER Fe/SILICALITE-2 CATALYST IL REDUCIBILITY OF K-Fe-MnO/SILICALITE-2 CATALYST

K_2O and MnO are two kinds of necessary promoters to theselective production of light alkenes from CO hydrogenation over silicalite-2(Si-2) zeolite supported Fe catalyst. The addition of both K_2O and MnOpromoters into Fe/Si-2 catalyst leads to a remarkable increase in the COconversion and the selectivity to light oletins. Silicalite-2 zeolite as Fe-MnOcatalyst support can suppress the formation of α-Fe_2MnO_3 or/andα-Fe_(2-y)Mn_yO_3 as Well as α-Fe_2O_3 and/or α-Mn_2O_3, being favorable for(?)ncreasing the dispersion of active metal component. So MnO can promotethe reduction of Fe~(3-) and enhance the capacity of CO adsorption, which canimprove the activity of the activity of the catalyst for CO hydrogenation. While K_2Opromoter is unfavorable for reduction of Fe~(3-) to some degree with formation of Fe~(2-) as a new species after reduction. However, K_2O promoter can enhance the capacity and strength of CO adsorption greatly.So K_2O can alsoimprove the activity of catalyst for CO hydrogenation.     

A stable metal-covalent-supramolecular organic framework hybrid: enrichment of catalysts for visible light-induced hydrogen production

Cubic metal-covalent-supramolecular organic framework(MCSOF-1)hybrid has been created from the reaction of two molecular components and subsequent co-assembly with cucurbit[8]uril(CB[8])in water.In the presence of CB[8],[Ru(bpy)_3]~(2+)-based acylhydrazine 1·2Cl reacted with aldehyde 2·Cl to quantitatively yield six-armed precursor 3·8Cl through the generation of MCSOF-1.MCSOF-1 combines the structural features of metal-,covalent-and supramolecular organic frameworks.Its periodicity in water and in the solid state was confirmed by synchrotron X-ray scattering and diffraction experiments.MCSOF-1could enrich discrete anionic polyoxometalates(POMs),maintain periodicity in acidic medium,and remarkably facilitate visible light-induced electron transfer from its[Ru(bpy)_3]~(2+)units to enriched POMs,leading to enhanced catalysis of the POMs for the reduction of proton to H_2in both aqueous(homogeneous)and organic(heterogeneous)media.     

Synthesis,Structure and Luminescent Properties of [Zn(btzb)2Cl2]·2H2O[btzb=1,2-Bis(5-tetrazolyl)benzene]

The title compound[Zn(btzb)2Cl2]·2H2O(1·2H2O,btzb=1,2-bis(5-tetrazolyl)benzene)was synthesized in situ by the[2 3] cycloaddition reaction of phthalonitrile with NaN3 in water in the presence of ZnCl2 under refluxing conditions.1·2H2O crystallizes in the monoclinic system,space group P21/c with a=9.0119(18),b=7.5566(15),c=18.076(5)(A),β=114.67(2)°,V=1118.6(4)(A)3,Z=2,Dc=1.784 g/cm3 T=223(2)K,C16H16N16O2Cl2Zn,Mr=600.74,F(000)=608,μ(MoKα)=1.393 mm-1,S=1.081,R=0.0306 and wR=0.0669 for 1896 observed reflections with Ⅰ ＞2σ(Ⅰ).The Zn2 ion of 1 is coordinated by four N atoms from two btzb ligands and two Cl atoms,forming a distorted octahedral coordination geometry.A number of intermolecular hydrogen bonding interactions between molecules 1 and/or the solvated water molecules result in a 3D hydrogen-bonded structure.The luminescent property of 1·2H2O was also investigated.     

Chiral cyanide-bridged 1D Fe~Ⅲ-Mn~Ⅲ heterobimetallic chains: Synthesis, structures and magnetic properties

Two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes: [Mn((R,R)-Salphen)Fe(Tp)(CN)3]n (1) and [Mn((S,S)-Salphen)Te(Tp)(CN)3]n (2) (Salphen = N,N’-1,2-diphenylethylenebis (salicylideneiminato) dianion, Tp = tris(pyrazolyl) hydroborate), [Mn((R,R)-Salphen)Fe(Tp*)(CN)3·2H2O]n (3) and [Mn((S,S)-Salphen)Fe(Tp*)(CN)3·2H2O]n (4) (Tp* = hydridotris (3,5-dimethylpyrazol-1-yl) borate), have been successfully synthesized by the reactions of MnIII schiff-base complexes with the tricyanometalate building block, [(LTp)Fe(CN)3]- (LTp = Tp or Tp*). All complexes are made up of neutral cyano-bridged zigzag double chains with (-Fe-C≡N-Mn-N≡C-)n as the repeating unit. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes. Magnetic studies demonstrate that ferromagnetic interactions are operative in these complexes. The ferromagnetic couplings become weak in the chains with the bending of the Mn-N≡C angles.     

N-H…X (X = F, Cl, Br, and I) hydrogen bonding in aromatic amide derivatives in crystal structures

Intramolecular N H···X (X=F, Cl, Br, and Ⅰ) hydrogen bonding patterns of aromatic amides in the solid state are summarized. It is revealed that the key for the formation of this kind of weak intramolecular hydrogen bonding in X-ray crystal structures is to suppress the competition of strong intermolecular N H···O C hydrogen bonding of the amide unit. For amides with identical backbones, the bonding capacity of halogen atoms as hydrogen bonding acceptors is in the order of F>Cl>Br>I, which is in accordance with their electronegativity strength. Generally, the five-membered hydrogen bonding is easier to form than the six-membered one.     

Lacunary Keggin Polyoxotungstate as Reaction-controlled Phase-transfer Catalyst for Catalytic Epoxidation of Olefins

A new reaction-controlled phase-transfer catalyst system, lacunary Keggin polyoxotungstate [C7H7N(CH3)3]9PW9O34 has been synthesized and used for catalytic epoxidation of olefins with H2O2 as the oxidant. Infrared spectra were used to analyze the behavior of the phase transfer of catalyst. In this system, the catalyst not only can act as homogeneous catalyst but also as heterogeneous catalyst to be easily filtered and reused. The epoxidarion reaction is clean and exhibits high conversion and selectivity as well as excellent catalyst stability.     

Zn~Ⅱ, Ni~Ⅱ, and Mn~Ⅱ Complexes Supported by N-Hydroxy-pyridine-2-carboxamidine: Syntheses,Structures, and Luminescent and Magnetic Properties

The employment of N-hydroxy-pyridine-2-carboxamidine in the coordination chemistry of zinc(Ⅱ), nickel(Ⅱ) and manganese(Ⅱ) under solvothermal conditions is reported. Four complexes of compositions, [Zn2(O2CMe)3{(py)C(NH2)NOH}4](OH)(1), [Zn4(OH)2{(py)C(NH2)-NO}4Cl2]·3MeCN(2), [Ni(SO4)(H2O){(py)C(NH2)NOH}2]·H2O(3) and [Mn(SO4){(py)C(NH2)-NOH}2]n(4), have been synthesized by rationally choosing different metal salts and dexterously employing acetate and sulfate ions as the bridging groups. Luminescent properties for 2 suggested strong emission in the solid state at room temperature. Variable temperature(2.0~300 K) magnetic studies for the linear chain complex 4 indicate weak antiferromagnetic Mn(Ⅱ)···Mn(Ⅱ) exchange interactions.     

Synthesis,Crystal Structure and Fluorescent Properties of Silver and Cadmium Complexes

Two new complexes [Ag(bix)]n·n NAA·n H_2O(1) and [Cd(NAA)(phen)_2(H_2O)]2· 2CH_3COO-·H_2O(2)(bix = 1,4-bis(imidazol-1-ylmethyl)benzene,HNAA = α-naphthylacetic acid,phen = 1,10-phenanthroline) have been successfully synthesized under hydrothermal conditions.Their structures have been determined by elemental analyses,IR spectroscopy,TG and single-crystal X-ray diffraction analysis.The intermolecular hydrogen bonding or π-π stacking interactions extend the complexes into a 3D supramolecular structure.Moreover,the luminescent properties of complex 2 have been investigated in the solid state.     

Simultaneous desulfurization and denitrogen of liquid fuels using two functionalized group ionic liquids

Deep desulfurization of liquid fuels is an important and challenging issue in worldwide petroleum refining industry.Extraction and catalytic oxidative desulfurization(ECODS)of liquid fuels using a series of ionic liquids(ILs)with two functionalized groups,such as[(CH2)2COOHmim]Cl/n Fe Cl3,[(CH2)2COOHmim]Cl/n Zn Cl2,and[Amim]Cl/n Fe Cl3,was studied.In the ECODS,the ILs were used as both extractant and catalyst and 30 wt%hydrogen peroxide(H2O2)solution as oxidant.The effects of molar ratios of[(CH2)2COOHmim]Cl(or[Amim]Cl)to Fe Cl3(or Zn Cl2)in ILs,H2O2/sulfur(O/S)molar ratio,reaction temperature,and the nature of sulfur compounds on sulfur removal were investigated.The natures of the functional groups(–COOH,–CH2–CH=CH2)in cations and the acid strength of anions play important roles in the ECODS and affect the reaction time,temperature,and desulfurization efficiency of different substrates.Also,nitrogen-containing compounds(pyridine,pyrrole,and quinoline)could be removed simultaneously in the ECODS and had different effects on dibenzothiophene removal.     

A facile synthesis of 2,4,6-trichloroborazine from boron trichloride-dimethylsulfide complex and ammonium chloride

<正>2,4,6-Trichloroborazine has been recognized as a desirable monomer for the preparation of high-performance boron nitride fibers through polymer derived ceramics route.So a high yield and facile synthesis of 2,4,6-trichloroborazine is essential in practice. Using boron trichloride-dimethylsulfide complex((CH_3)_2S·BCl_3) and ammonium chloride(NH_4Cl) as starting materials and toluene(C_6H_5CH_3) as solvent,the synthesis of 2,4,6-trichloroborazine to give high yield is reported.     

Synthesis and Crystal Structure of 7-((7S)-7-Aminospiro[2.4]heptan-5-yl)-8-chloro-6-fluoro-1-((1R,2S)-cis-2-fluorocyclopropyl)-4-oxo-1,4-dihydroqun-oline-3-carboxylic Acid Fumaric Acid Monohydra

A new compound [C_(19)H_(19)N_3O_3F_2Cl·C_4H_3O_4·H_2O](I),(7-((7S)-7-aminospiro[2.4]heptan-5-yl)-8-chloro-6-fluoro-1-((1R,2S)-2-fluorocyclopropyl)-4-oxo-1,4-dihydroquinoline-3-carboxylic acid fumaric acid monohydrate), was synthesized and structurally characterized by single-crystal X-ray diffraction, 1H NMR, 14 C spectra and mass spectra. I crystallizes in monoclinic, space group P21/c with a = 8.495(2), b = 12.545(3), c = 11.832(3) ?, β = 103.37(1)°, V = 1226.8(5) ?3, Z = 2, Mr = 543.90, Dc = 1.472 g/cm3, F(000) = 564, μ = 0.225 mm-1, the final R = 0.0307 and w R = 0.0892 for 6886 observed reflections with I 2σ(I). X-ray diffraction analysis reveals that the quinolinone ring is almost coplanar, and the pyrrole ring adopts an envelope form. Packing of crystal I is constructed and stabilized by the N–H···O, O–H···O and N–H···Cl hydrogen bonds together with C–H···π interations.