Syntheses of Two Chiral Clusters [η5—C5H4C（NR）CH3]—RuNiM（CO）5（μ3—S）（R=NH—C6H3—2,4—（NO2）2,M=Mo,3;M=W,4）and the Single—crystal Structure of Cluster 3

1 INTRODUCTION The synthesis of chiral clusters containing four different atoms at the vertexes of the tetrahedron has been extensively studied because the chiral cluster can induce an asymmetric catalysis potentially[1]. Until now, many tetrahedron-type chiral clusters have been reported, but only a few of the reactions about the organic group in these clusters were investi- gated[2～4]. In this paper, we described the syntheses of clusters 3 and 4, and the structure of the former. 2 …     

Synthesis and Structure of [Er4（μ3—OH）4（Hpro）4（Pro）2（H2O）7]（ClO4）6.7H2O

1 INTRODUCTION The design and synthesis of polynuclear com- plexes have attracted chemists?attention in the contemporary chemistry, since their clusters maybe lead to novel materials with magnetic, optical, electronic and catalytic properties of the constituent metals[1～3]. It is also prevalently interesting to synthesize high-nuclearity metal complexes for their nanoscopic dimensions[3, 4]. Spectroscopic properties of the lanthanides are widely used in the study of biological systems. …     

Syntheses and Anti—inflammatory Actiobn of （η—C5H5）2Ti （Cin）2 and （η—C5H5）2Ti（Tzea）2

Two new Complexes(Cp)2Ti(Cin)2and (CP2)Ti(Tzea)2(CP=Cyclopentadienyl η^5-C5H5)have been synthesized in THF by the reaction of HCin(Cincofen,2-phenylquinoline-4-carboxylic acid)or HTzea(5-phenyltetrazolyl-2-ethanoic acid)with(Cp)2TiCl2,and characterized by elemental analyses,IR,1H NMR and 13C NMR,UV spectra,molar conductivity,TGDTA.In the complexes the carboxyl groups are coordinated to Ti(IV)in a monodentate manner,The inhibitory actions of the complexes on mice ear tumefaction caused by croton oil and the rat foot granulation growth produced by cotton wool are higher than those of the corresponding ligands HCin,HTzea and [(Cp)2TiCl2],while their toxicities are lower than those of the free ligands.ηη     

Synthesis of Substituted Indenyl Lanthanide Chloride and Molecular Structure of[（C5H9C9H6）2Yb（μ—Cl）2Li（Et2O）2]

Reaction of anhydrous ytterbium trichlorides with 2 equiv.of cyclopentylindenyl lithium in THF solution,followed by removal of the solvent and crystallization of the porduct from diethyl ether,affords a crystal complex of the composition(C5H9C9H6)2Yb(μ-Cl)2Li(Et2O)2.Crystallographic analysis shows that the ytterbium coordinated by two cyclopentylindenly rings and lithium surrounded by two ether molecules are bridged by the two chlorine atoms and Yb,Li and two chlorine atoms form a plane.     

Preparation, characterization, and catalysis of mecro-catalysts

Because catalysis by metals is a surface phenomenon, many technological catalysts contain small (typically nanometre-sired) supported metal particles with a large fraction of the atoms exposed. Many reactions, such as hydrocarbon hydrogenations, are structure-insensitive, proceeding at approximately the same rates on metal particles of various sizes provided that they are larger than 1 nm and show bulk-like metallic behavior. But the catalytic properties are not known when metal particles become so small that their sizes are indium clusters consisting of several indium atoms. Here the catalytic behavior of precisely defined clusters of just four and six indium atoms on solid supports is shown. It is found that the Ir4 and Ir6 clusters differ in catalytic activity both from each other and from metallic Ir particles.     

Synthesis and Characterization of [NH3（CH2）2NH2（CH2）2NH3]BiCl6

1 INTRODUCTION During the past decade, a series of organic-inor- ganic hybrid compounds based on metal halide units have been prepared and studied[1]. The combination of organic and inorganic components at the mole- cular level affords us the opportunity to design new hybrid materials and modulate the properties of components[2]. As a result, some interesting proper- ties, such as non-linear optical[3], interesting magne- tic[4], efficient luminescence[2], ideal thermal and mechanical sta…     

Studies on the Electronic Structures and Spectra of C78（CH2）3

The structures and spectra of 20 possible isomers of C78(CH2)3 have been studied by using AM1,INDO/CIS and DFT methods. The results show that the most stable isomer is 1,2,3,4,5,6-C78(CH2)3 (A) with annulene structures,where three -CH2 groups are added to the 6/6 bonds located at the same hexagon passed by the shortest axis of C78 (C2v). Compared with that of C78 (C2v),the first absorption in the electronic spectrum of C78(CH2)3 (A) is blue-shifted because of its wider LUMO-HOMO energy gap. While the IR frequencies of the C–C bonds on the carbon cage are red-shifted owing to the formation of annulene structures and the extension of the conjugated system. The chemical shifts of the carbon atoms in 13C NMR spectra are moved upfield upon the addition.     

Synthesis and Crystal Structure of Dichlorodianiline Palladium （Ⅱ） （C6H5NH2）2PdCl2

1 INTRODUCTION Palladium compounds have attracted much attention as a consequence of their application in homogeneous and heterogeneous catalyses[1]. For instance, palladium compounds are the most active catalysts for the carbonylation, such as palladium-catalyzed carbonylation of nitroarenes, aryl halides, alkyne and so on[2～4]. Some dramatic results in the homogeneous catalysis of the reactions of organic compounds, particularly the successful commercial exploitation of the Wacker on…     

Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2]

Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.     

Synthesis and Structural Characterization of Pd[CH3O（O）C6H3CHNNC（S）NH2]（C5H5N）

1 INTRODUCTION Palladium (Ⅱ) coordination and organometallic compounds usually show square planar environments at the metal center[1], and have experienced an im- portant development in the past years due to their acting as intermediates in different types of catalytic reactions and numerous applications in organic synthesis[2]. Although palladium plays an increase- ingly recognized role as a biometal[3], little is known about the structure and function of palladium compounds in living …     

Synthesis and Structure of [Cu（OH）2（H2O）2（4—C5H4N—COOH）2]

1 INTRODUCTION Supramolecular chemistry and crystal engineering of coordination compounds have attracted considerable interests nowadays owing to the fascinating structural diversity and potential applications as functional materials[1,2]. Generally, architectures of supramolecules are formed through hydrogen bonds, ?- ?stacking interaction or other weak interactions between the molecules. Recently, many supramolecular compounds containing silver(I) and copper(II) species have been re-…     

Gas Phase Selective Catalytic Oxidation of Toluene to Benzaldehyde on V2O5-Ag2O／η-Al2O3 Catalyst

Gas phase selective catalytic oxidation of toluene to benzaldehyde was studied on V2O5-Ag2O/η-Al2O3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM,and FT-IR. The catalytic results showed that toluene conversion and selectivity for benzaldehyde on catalyst sample No.4 (V/(V Ag)=0.68) was higher than other catalysts with different V/Ag ratios. This was attributed to the higher surface area, larger pore volume and pore diameter of the catalyst sample No.4 than the other catalysts. The XRD patterns recorded from the catalyst before and after the oxidation reaction revealed that the new phases were developed, and this suggested that silver had entered the vanadium lattice. XPS results showed that the vanadium on the surface of No.4 and No.5 sample was more than that in the bulk, thus forming a vanadium rich layer on the surface. It was noted that when the catalyst was doped by potassium promoter, the toluene conversion and selectivity for benzalde hydewere higher than those on the undoped catalyst. This was attributed to the disordered structure of V2O5 lattice of the K-doped catalyst and a better interfacial contact between the particles.     

Synthesis and Crystal Structure of CoCl（ieaa）（C10H7—ieai）（C10H7NH2）

1 INTRODUCTION A number of isonitroso-b-diketones and isonitroso-b-ketoesters such as isonitrosoacetyl- acetone(Hiaa), isonitrosobenzoylacetone(Hiba) and isonitrosoethylacetoacetate (Hieaa) have been employed as reagents in spectrophotometric determination of iron, palladium and ruthenium[1]. Transition metal complexes of such ligands[2] are potential models for metal binding sites in ferroverdin[3]. They were found as dyes and light-absorbing agents for the acceleration of the sol…     

Synthesis and Characterization of the Chiral Skeleton Cluster [NiRuMo(CO)_5(μ_3-S)(η~5-C_5H_5)(η~5-C_5H_4COCH_3)]

1 INTRODUCTION The chemistry of transition metal cluster has enjoyed an exceptional growth since the mid 1970s[1, 2], especially in recent years the structural and bonding aspects of mixed-metal tetrahedral skeleton clusters have been extensively studied[3]. One important reason is that such chiral cluster can induce an asymmetric catalysis potentially. In our research group, considerable efforts have been directed to the synthesis of chiral tetrahedral clusters containing four different…     

Synthesis and Structure of Bis（indene—1,2,3—trione 2—oximato）bis （aqua）Mn（Ⅱ）：Mn（C9H4NO3）2（H2O）2

1 INTRODUCTION The interest in the complexes of transition metals with ligands ketoxime[1, 2] as potential models for metal binding sites in ferroverdin[3, 4] has prompted the investigation on the structures and the overall coordination geometry of the metal centers in these complexes. Oxime derivatives are interesting ligands since the ketoximes are found to chelate transition metals through the N (oxime) and O (ketone) atoms[5, 6]. However, monodentate coordination via only one O or …     

Synthesis and Crystal Structure of （2S,5S）-1-Aza-2-（2-pyridyl）-3-oxa-4,4-diphenylbicyclo [3.3.0] Octane

1 INTRODUCTION The catalytic asymmetric synthesis has been a challenging subject in organic synthesis. The deve- lopment of efficient enantioselective catalysts appli- cable to a wide range of carbon-carbon bond form- ing reactions represents a pivotal …     

CRYSTAL STRUCTURE OF MOLYBDENUM-CARBENE COMPLEX (CO)_5Mo=C(OC_2H_5)C_6H_4-p-CH_3

<正> INTRODUCTION. Recently, researches on carbene metal complexes are very active, as they are of great importance in both theoretical study and catalytic activity. In a systematic research, the crystal structure of the title complex was analyzed and reported here to the advantage of understanding the catalytic action and searching for new and better carbene catalysts of novel kinds.     

Coordination Triangular Prism of Bisilver Complex with Triply—bridged of Bis（diphenylphosphino）amine

1 INTRODUCTION Recently coinage metal complexes of poly- dentate phosphines are of great interest owing to the applications in diverse areas such as supramolecular design, photophysics and catalysis[1～4]. It is well- known that the binuclear coinage metal complexes of diphosphine [M2(diphosphine)2(MeCN)2]2+ (M = Cu, Ag, Au)[5～16] are excellent precursors for the design of polynuclear or polymeric materials with desired properties due to the easy substitution of weakly coordinated ac…     

Impact of Water Molecules on the Isomerization of CH3S（OH）CH2 to CH3S（O）CH3： A Computational Investigation

The isomerization of CH3S（OH）CH2 to CH3S（O）CH3 in the absence and presence of water has been investigated at the G3XMP2//B3LYP/6-311 ＋ G（2df, p） level. The naked isomerization, the reaction without water, gives the high barrier height （21.56 kcal.mol^-1）. Three models are constructed to describe the water influence on the isomerization, that is, water molecules are the catalyst and the microsolvation, and water molecules act as the catalyst and microsolvation simultaneously. Our results show that the isomerization barrier heights of CH3S（OH）CH2 to CH3S（O）CH3 are reduced by 12.32, 11.04, and 7.80 kcal.mol^-1, respectively, when one, two, and three water molecules are performed as catalyst, in contrast to the naked isomerization. Moreover, the rate constants of the isomerization are calculated using the transition state theory with the Wigner tunneling correction over the temperature range of 240-425 K. We find that the rate constant of a single water molecule as the catalyst is 1.58 times larger than the naked isomerization at 325 K, whereas it is slower by 6 orders of magnitude when water molecule serves as the microsolvation at 325 K, compared to naked reaction. So the water-catalyzed isomerization of CH3S（OH）CH2 to CH3S（O）CH3 is predicted to be the key role in lowering the activation energy. The isomerization involving water molecules acting as mierosolvation is unfavorable under atmospheric conditions.     

Synthesis and Crystal Structure of Cadmium（Ⅱ） Complex [Cd（H2O）（CH3OC6H4COO）2]n

1 INTRODUCTION Cadmium (Ⅱ) complexes have been exten- sively studied from both chemical and structural views, mainly due to the capability of cadmium (Ⅱ) (shared by most d10 metal ions) to adopt different modes of coordination determined by the consideration of size, as well as electrostatic and covalent bonding forces[1]. And the field of coordination polymers has witnessed tremendous growth over the last decade[2]. Many coordination polymeric networks have been shown to posses intere…