Catalytic epoxidation of olefin over supramolecular compounds of molybdenum oxide clusters and a copper complex

The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.

Model Compounds of the Mn Cluster in Oxygen-evolving Complex of PSⅡ

Six model compounds have been synthesized and used for probing the structural features of the Mn cluster in oxygen_evolving complex (OEC) of photosystem Ⅱ (PSⅡ). The model compounds contain Mn 2(μ_O) 2 and μ_O_μ_carboxylato di_manganese structural units, which offer Mn—Mn, Mn……Mn, and Mn—O(N) structural parameters consistent with the corresponding data of the OEC in PSⅡ, implying that the Mn cluster in OEC may possess similar structural features. Two model compounds containing halide anion have been used for discussing the binding of Cl - to Mn in PSⅡ. It is suggested that in the five S states, ligand exchange would lead to the ligation of chloride to Mn in the S states with Mn of higher valence.

Preparation for Supramolecular Complexes of Chiral Diols BDPDD, DMBDPD and BINOL with Some Prochiral Compounds

Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral guests, a, b-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.

Structure Studies on New Types of Macrocyclic Compounds Part V．Crystal Structure of Nickel（II） Complex of 5，12－Diphenyl－7，14－dimethyl－1，4，8，11－tetraazacyclotetradecane－N＇，N－diacetic Acid

Crystal structure of nickel（II） complex with a new 14 membered tetraazamacrocyclic ligand 5,12-diphenyl-7,14-dimethyl-1,4,8,11-tetraazacyclotetradecane-N’,N-diacetic acid,Ni[N4C10（CH2COO）2（C6H5）2]·2H2O, Mr= 589. 38 is reported.It crystallizes in monoclinic P21/c space group with a=12.949（6）,b=16.373（3）,c=14.232（16）,β=98.68（6）°,V=2982.9（7）,Z=4,Dc=1.312 gcm-3,μ=6.953 cm-1,F（000）=1256.0.Finally,the structure was refined to R=0.080,Rw=0.065 for 2952 reflections.The central nickel ion of the complex forms an octahedron with four nitrogen atoms of the macrocycle and two oxygen atoms of the appended carboxylate groups.Two phenyl planes of the ligand are almost parallel to each other.

THE FORMABILITY OF COMPLEX FLOURIDE COMPOUNDS

The formability of complex flourides has been studied by chemical bond parameter-pattern recognition method. In a multi-dimensional space spanned by ionic radius, ionic polarizability, electronegativity and ionic charge of the metal elements, the binary complex flouride-forming systems and binary flouride systems without complex flouride formation distribute in different regions with a clear-cut boundary. The mathematical models obtained are useful for new complex flouride predicton.

Examination of Polymeric Azomethine Compounds and Their Transition Metal Complexes by Using XRF and XRD Technique

In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.

Syntheses of Coordination Compounds of 2-Amino-3-Methylbutanoic Acid Their Mixed Ligand Complexes and Antibacterial Activities

Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-phenantroline and ethylenediamine were further synthesized, M:L, (1:2). These compounds were characterized using electronic, infra-red spectrophotometry, magnetic susceptibility measurement and percentage metal analyses. The zones of inhibition and minimum inhibitory concentrations of the compounds against eight microbes were studied. The results obtained indicated an octahedral geometry for the Cr(III) complexes, indicative of additional coordination of two water molecules. On the other hand a square pyramid geometry was obtained for the binary oxovanadium complex and its 1,10-phenantroline adduct. However, for the oxovanadium ethylenediamine adduct a distorted octahedral geometry was proposed. The result for the antibacterial studies indicated that both mixed ligand complexes of 1,10-phenantroline exhibited good antibacterial activity, and in some cases better activity than the standard, streptomycin.

Syntheses, Characterization and Biological Activity of Coordination Compounds of 3-Hydroxy-2-methyl-4<i>H</i>-pyran-4-one and Its Mixed Ligand Complexes with 1,2-Diaminocyclohexane

Coordination compounds of 3-hydroxy-2-methyl-4H-pyran-4-one with iron(III), cobat(III) and chromium(III) were synthesized with M:L (1:2). Mixed ligand coordination compounds of 3-hydroxy-2-methyl-4H-pyran-4-one and 1,2-diaminocyclohexane using the same metal ions were also synthesized M:L1:L2 (1:1:1) where L1 is 3-hydroxy-2-methyl-4H-pyran-4-one and L2 is 1,2-diaminocyclohexane. The coordination compounds obtained were characterized using electronic and infrared spectral analyses, magnetic susceptibility and percentage metal analysis. They were also evaluated for their cytotoxic and antioxidant activities. The result obtained suggested that octahedral geometry was obtained for all the compounds, as a result of additional two molecules of the solvent coordinated to the metal ions. Both the primary and secondary ligands coordinated in a bidentate fashion. The synthesized compounds exhibited moderate cytotoxicity, although none was as active as the standard. The cobalt(III) mixed ligand complex elicited the highest activity. The synthesized compounds all exhibited good to moderate antioxidant activity.

STUDIES ON ORGANO-MOLYBDENUM AND TUNGSTEN COMPOUNDS(Ⅲ)——CATALYTIC POLYMERIZATION OF ACETYLENE BY M-O-C BOND-CONTAINING COMPLEXES OF Mo AND W

Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymerization of monosubstituted acetylene.The catalytic mechanism has been preliminarily discussed.It is suggested that the active species be metal-car-bene.In our previous publications we reported the synthesis of some new Fischer's molybdenum and tungsten-carbene complexes and catalytic activity for alkyne polymerization.The results show that the activity of Fischer's molybdenum-carbene is higher than that of tungsten.The catalytic polymerization of alkyne by M-σ-c bond-containing complexes of molybdenum and tungsten has not been reported yet in literature.Therefore,four M-σ-C bondontaining complexes of molybdenum and tungsten were synthesized by using the method reported in the literature,and catalyst polymerization of alkyne by these complexes was examined.

STUDIES ON SOLID STATE REACTIONS OF COORDINATION COMPOUNDS(LXⅡ)Solid state synthesis and crystal structure of the complex ICu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)CIJ·0.5CS_2

[Cu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)Cl]·0.5CS_2=,Mr=895.79,monoclinic,space group P2_1/a,a=17.231(3),b=14.611(2),c=18.000(3) ,β=105.56(2)°,V=4365(1) ~3, Z=4,D_c=1.37g/cm^3.,λ(MoK_α)=0.71073 ,μ=12.15cm^(-1),F(000)=1855,R=0.052, R_W=0.045 for 3930 observed reflections with Ⅰ>1.5σ(Ⅰ).The central metal atom has a dis. torted tetrahedral geometry with bond lengths Cu-S=2.384(2) (Au-S=2.389(4)), Cu-Cl=2.481(3)(Au-Cl=2.474(1))and Cu-P=2.269(2)-2.289(2)(Au-P=2.270(4)-2.279(4)) .

CHARACTERIZATION OF SOME SCHIFF BASES OF HETEROCYCLIC COMPOUNDS AND THEIR TRANSITION METAL COMPLEXES

Some new Schiff bases were synthesized by the condensation of equimolar quantities of salicylaldehyde and 2-amino-5-phenylazo-pyridine or its derivatives in dry benzene(1):Metal complexes of the type ML_2and M'L_3 where M=Cu^(2+),Co^(2+),Ni^(2+),Mn^(2+)Pd^(2+),M'=Fe^(3+)and L=different newly synthesized monobasic Schiff bases were prepared in absolute ethanolic medium(2)and characterized by elementary analysis,conductance measurements,infrared spectra,electronic spectra,magnetic moments studies.

Structure Studies on New Types of Macrocyclic Compounds Part Ⅵ. Crystal Structure of Copper(Ⅱ) Complex of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-N', N'-diaceticacid

The crystal structure of copper(Ⅱ) complex with a new 14-membered tetraazamacrocyclic ligand 5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane-N'N'-diacetic acid,[CuC16N4H34(CH2COO)(CH2COOH)]·ClO4·0. 5HCIO4·1. 5H2O was determined. Crystallographic data: Mr = 639.22,orthorhombic, space group Pcnb with a=11.743(4),b=16.446(2),c=29.611 (4) A,Z=8,V=5726(3) A3, Dc=1.482 g·cm-3, F(000)=1344,μ=9. 64 cm-1,R=0.063,and Rw=0.067 for 2386 reflections with I≥3σ(I). The structure shows an unusual configuration in which two carboxyl groups were bonded to two neighboring nitrogen atoms of the macrocycle, N1 and N4, and six methyl substituents occur on one side of the macrocycle, while two carboxyl groups on the other side, and central copper(Ⅱ) ion forms a five-coordinated geometry.

Wear-Resistance Performance of ZA-27 Alloys Reinforced by Rare Earth Compounds

The morphology of ZA-27 alloy reinforced by RE compounds and its wear-resistance were studied. It is found that some nodular second phases appear due to the addition of Si and RE, which can disperse in grain boundaries or between dendrite crystals so that the alloy has been refined. Energy spectrum analysis of scanning electron microscope shows that the second phases are complex compounds containing RE, Al, Zn and Si. The micro- hardness test indicates that micro-hardness values of the compounds are higher than those of the matrix. The wear-resis tance of ZA-27 alloy reinforced by RE compounds is 4 times as high as that of ZA-27 alloy and also higher than that of ZA-27 alloy containing Si phase. The impact toughness of the alloy containing RE and Si is higher than that of the alloy containing Si.

Mid-Temperature Synthesis of CeO_2-TiO_2 Complex Compound and Its XRD Structure Study

The CeTi 2O 6, which is formed above 1300 ℃ by ceramic method, was obtained at 700 ℃ using sol gel synthesis method. XRD analysis shows that there is 8% deficient of Ce in the structure. The chemical formula is Ce 0.92 Ti 2O 5.84 , which has a monoclinic structure with space group of C 2/ m . Its cell parameters are a =0.9811(8) nm, b =0.3726(3) nm, c =0.6831(6) nm, and β =118.84°. After being treated at 1300 ℃ for 3 h, the system keeps stable but the deficient disappears, while the chemical formula change to the normal CeTi 2O 6, and the cell parameters are a =0.9813(3) nm, b =0.3752(4) nm, c =0.6883(5) nm, β =119.05°. The key to synthesis the precursors of CeTi 2O 6 is that Ti 4+ and Ce 3+ ions must reach the atomistic distributing state and prevent the oxidation of Ce 3+ during sol gel process.

Crystal Structure of the Addition Compound of N,N′-Bi(2-pyridylmethyl)-Oxamide and the Complex of Copper with 1,10-Phenanthroline

The structure of addition compound Cu(phen)3(PMoxdH)(CO4)2 was establish ed by means of X-ray crystallography,where PMoxdH is N,N-Bi(2-pyridyl-methyl)-oxamide,in which six nitrogen atoms of the three 1,10,-phen-anthroline bind to the copper ion and the oxygen atom of PMoxdH is uncoordinated.

Preparation and Characterization of Layered Compound Zirconium Bis(monohydrogenphosphate) Intercalated with Rare Earth Complex

Layered compound zirconium bis(monohydrogenphosphate)(alpha-ZrP) intercalated with rare earth complex Eu(DBM)(3)phen was prepared. The pre-intercalation of p-methoxyaniline into alpha-ZrP makes the interlayer separation large enough to exchange PMA with europium complex, thus, the luminescent assembly was prepared. This was confirmed by X-ray diffraction, UV-visible spectra and elemental analysis. The fluorescence spectra and lifetime of the assembly were also presented.

Simulation calculation of solubility of insoluble compound M_mA_a in complex system

A simulation calculation model for the solubility of insoluble compound MmAa in complex system was established.According to coordination equilibrium principle,relevant dissociation reaction,complexation reaction,self-complexation reaction and protonation reaction during insoluble compound dissolving were considered and then the mass balance equations about solubility calculation were obtained.In the case analysis,the solubility of silver chloride in ammonia system was obtained by simulation calculation,and curved surface charts of thermodynamic equilibrium about the total concentration of silver ions,pH and concentration of ammonia ions were drawn correspondingly.The results show that under the conditions of room temperature and 6 mol/L ammonia concentration,the calculated solubility value of silver chloride(34 g/L) is close to the actual value(31 g/L),demonstrating that this model is suitable for solubility calculation of insoluble compound MmAa in the complex system.

Ultra-deep Removal of Metal Ions from Coal Tar by Complexation:Experimental Studies and Density Functional Theory Simulations

As one of the important aspects of upgrading coal tar,the ultra-deep removal of metal ions via the complexation method was investigated by screening four complexing agents and performing density functional theory(DFT)simulations.Analysis of the compositions and contents of the metallic compounds in the coal tar revealed that the main components were iron and calcium naphthenates.Direct filtration reduced the mechanical impurity content from 0.24%to 0.0752%,indicating that most of the large particles could be easily removed.Among the four complexing agents,namely,acetic acid,oxalic acid,citric acid,and ethylenediaminetetraacetic acid,oxalic acid exhibited the best demetallization performance.The DFT simulations suggested that the high performance of oxalic acid originated from its 1:1 coordination mode,rigid dicarboxyl structure,and greater binding energy.