The Effect of the Oxygen Preadsorption on the Adsorption of Nitric Oxide on Mo (111)

The adsorption of nitric oxide adsorption on clean Mod(111), Mo(111)/O2-(4×4), Mo(111)/O2-(1×3), Mo(111)/O2-(112) facets and Mo(111) oxide surfaces was studied. Mass 28 (N2) desorption spectra show two high temperature peaks at approximate 1030 (β1) and 1200K (β2). For NO exposures less than 0. 1 L only the ft peak was observed. At higher exposures, the ft peak appeared and small amounts of N2O as well as NO desorbed. The preadsorption of oxygen blocked the β2 desorption partially on the (4×4) and (1×3) surfaces and fully on the (112) facet and oxide surfaces. In addition, the β1 desorption peak shifted to higher temperatures with increasing oxygen preexposure.     

中药升麻的化学成分II. 升麻酰胺的化学结构

自兴安升麻(Cimicifuga dahurica)根茎分得一个新的桂皮酰胺衍生物, 命名为升麻酰胺(cimicifugamide, 1)经解析其IR、MS、1^H和13^C NMR、1^H-1^H COSY、1^H-1^H NOESY、13^C-1^H COSY、13^C-1^HCOLOC及选择性远程DEPTN图谱, 确证其结构为N-(3'-甲氧基-4'-羟基苯乙基)-4-O-β-D-吡喃半乳糖-阿魏酰胺。     

Simple Approach to the Highly Stereoselective Synthesis of trans-1,2-Cyclopropane Derivatives

In the presence of KF·2H2O, furoylmethyltriphenylarsonium bromide （1a） or thienoylmethyltriphenylarsonium bromide （1b） reacted with 2-[（un）substituted benzylidene]malononitrile （2） in chloroform at room temperature to give trans-3,3-dicyano-1-furoyl-2-[（un）substituted phenyl]cyclopropane （3a） or trans-3,3-dicyano-1-thienoyl-2- [（un）substituted phenyl]cyclopropane （3b） respectively in good yield with high stereoselectivity. The structures of product 3 were confirmed by IR, MS, 1^H NMR, 1^H-1^H COSY and microanalysis. The relative configuration of product 3 was determined by 1^H-1^H NOESY technique. The mechanism for the formation of product 3 was also proposed.     

中药升麻的化学成分II. 升麻酰胺的化学结构

自兴安升麻(Cimicifuga dahurica)根茎分得一个新的桂皮酰胺衍生物, 命名为升麻酰胺(cimicifugamide, 1)经解析其IR、MS、1^H和13^C NMR、1^H-1^H COSY、1^H-1^H NOESY、13^C-1^H COSY、13^C-1^HCOLOC及选择性远程DEPTN图谱, 确证其结构为N-(3'-甲氧基-4'-羟基苯乙基)-4-O-β-D-吡喃半乳糖-阿魏酰胺。     

含酚醚中心功能基的大二环型穴醚的合成及配位性能

4-氯-2, 6-二羟基苯甲醚(2)与氯乙酸钠缩合, 制得4-氯-2, 6-二(羟甲氧基甲基)苯甲醚(4), 由4经酰氯化生成4-氯-2, 6-二(3-氯甲酰基-2-氧杂丙基)苯甲醚(5)后, 再与相应的二氮杂冠醚3a, 3b和3c反应制备标题化合物1a~1c。用1^H NMR法研究了1a~1c对碱金属离子的配位性能, 讨论了分子内的中心功能基和底环大小对其IR, 1^H NMR和配位行为的影响。     

Phenolic compounds from the aqueous extract of Acacia catechu

From the aqueous extract of Acacia catechu,two new phenolic compounds(3R,4R)-3-(3,4-dihydroxyphenyl)-4-hydroxycy-clohexanone (1) and(4R)-5-(1-(3,4-dihydrophenyl)-3-oxobutyl)-dihydrofuran-2(3H)-one(2) were obtained.Their structures were determined on the basis of spectroscopic analysis.Free-radical scavenging activities of them were evaluated.     

Studies on Synthesis and Photochromism of a Novel Class of Fulgimide： （Z）-4-Oxazolylfulgimide

A novel class of fulgimide, (Z)-4-oxazolylfulgimide ((Z)-1-benzyl-4-isopropylidene-3-[1-(2-aryl-5-methyloxazolyl)ethylidene]tetrahydropyrrole-2,5-dione), was synthesized by the reaction of (Z)-4-oxazolyl fulgide (4-isopropylidene-3-[1-(2-aryl-5-methyloxazolyl) ethylidene]tetrahydrofuran-2,5-dione) with benzyl amine. Photochromic property of (Z)-4-oxazolylfulgimide was studied. Compared with (Z)-4-oxazolylfulgide, the absorption maximum of the colored form of (Z)-4-oxazolylfulgimide is bathochromic-shifted. Substituents on the aryl ring affect the absorption maximum of the open form and the colored form of (Z)-4-oxazolylfulgimide.     

Three new diarylheptanoids and their antioxidant property

Three new diarylheptanoids,i.e.,sodium(5S,2E)-1,7-bis(4-hydroxyphenyl)-1-hydroxy-2-hepten-5-sulfonate(1), sodium(5R,2E)-1,7-bis(4-hydroxyphenyl)-1-hydroxy-2-hepten-5-sulfonate (2) and 3,5-diacetoxy-1-(3-methoxy-4,5-dihydroxy- phenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane (3) were isolated from the rhizomes of Zingiber officinale.The structures of the new compounds were elucidated on the basis of spectroscopic methods.The antioxidant activities of 3 were assayed by in vitro models involving DPPH free radicals and superoxide anion radicals.     

Two New Isobutyltartrate Monoester from Coeloglossum viride （L.） Hartm.var.bracteatum（Willd.） Richter

Two new isobutyltartrate monoesters,coelovirin A (1) and B(2),were isolated from the rhizomes of Coeloglossum viride (L.) Hartm. var. bracteatum (Willd.) Richter (Orchidaceae). Their structures were elucidated as (2R,3S)-2-isobutyltartrate-1-(4-β-D-glucopyranosyloxybenzyl) ester 1 and (2R,3S)-2-isobutyltartrate-4-(4-β-D-glucopranosyloxybenzyl) ester 2 on the basis of physical constants and spectroscopic methods including 2D NMR techniques.     

DFT Investigations About Pyrazine Molecules on Si(100)-2×1 Surface

It is important to understand the interface of aromatic molecules on semiconductor surfaces because of the rich functionality of such molecules on semiconductor surfaces.The chemisorption of pyrazine molecules on the Si(100)-2×1 surface has been investigated using the B3LYP density functional theory with Si9H12 one-dimer and Si15H16 two-dimer cluster models.The calculated results predict that N-dative bonded-state,C2-C5 [4 2] and the tight-bridge1,2,5,6 products may coexist on the Si(100)-2×1 surface.     

Bimetallic carbonyl thiolates as functional models for Fe-only hydrogenases

The anion [Fe(2)(S(2)C(3)H(6))(CN)(CO)(4)(PMe(3))](-) (2(-)) is protonated by sulfuric or toluenesulfonic acid to give HFe(2)(S(2)C(3)H(6))(CN)(CO)(4)(PMe(3)) (2H), the structure of which has the hydride bridging the Fe atoms with the PMe(3) and CN(-) trans to the same sulfur atom. (1)H, (13)C, and (31)P NMR spectroscopy revealed that HFe(2)(S(2)C(3)H(6))(CN)(CO)(4)(PMe(3)) is stereochemically rigid on the NMR time scale with four inequivalent carbonyl ligands. Treatment of 2(-) with (Me(3)O)BF(4) gave Fe(2)(S(2)C(3)H(6))(CNMe)(CO)(4)(PMe(3)) (2Me). The Et(4)NCN-induced reaction of Fe(2)(S(2)C(3)H(6))(CO)(6) with P(OMe)(3) gave [Fe(2)(S(2)C(3)H(6))(CN)(CO)(4)[P(OMe)(3)]](-) (4). Spectroscopic and electrochemical measurements indicate that 2H can be further protonated at nitrogen to give [HFe(2)(S(2)C(3)H(6))(CNH)(CO)(4)(PMe(3))](+) (2H(2)(+)). Electrochemical and analytical data show that reduction of 2H(2)(+) gives H(2) and 2(-). Parallel electrochemical studies on [HFe(2)(S(2)C(3)H(6))(CO)(4)(PMe(3))(2)](+) (3H(+)) in acidic solutions led also to catalytic proton reduction. The 3H(+)/3H couple is reversible, whereas the 2H(2)(+)/2H(2) couple is not, because of the efficiency of the latter as a proton reduction catalyst. Proton reduction is proposed to involve protonation of reduced diiron hydrides. DFT calculations establish that the regiochemistry of protonation is subtly dependent on the coligands but is more favorable to occur at the Fe-Fe bond for [Fe(2)(S(2)C(3)H(6))(CN)(CO)(4)(PMe(3))](-) than for [Fe(2)(S(2)C(3)H(6))(CN)(CO)(4)(PH(3))](-) or [Fe(2)(S(2)C(3)H(6))(CN)(CO)(4)[P(OMe)(3)]](-). The Fe(2)H unit stabilizes the conformer with eclipsed CN and PMe(3) because of an attractive electrostatic interaction between these ligands.     

Triazenide-bridged rhodium-palladium complexes: [I2Rh(mu-p-MeC6H4NNNC6H4Me-p)2Pd(eta(3)-C3H5)]-, a stable paramagnetic [RhPd]4+ species with a localised Rh(II) centre

Deprotonation of mixtures of the triazene complexes [RhCl(CO)2(p-MeC6H4NNNHC6H4Me-p)] and [PdCl(eta(3)-C3H5)(p-MeC6H4NNNHC6H4Me-p)] or [PdCl2(PPh3)(p-MeC6H4NNNHC6H4Me-p)] with NEt3 gives the structurally characterised heterobinuclear triazenide-bridged species [(OC)2Rh(mu-p-MeC6H4NNNC6H4Me-p)2PdLL'] {LL' = eta(3)-C3H5 1 or Cl(PPh3) 2} which, in the presence of Me3NO, react with [NBu(n)4]I, [NBu(n)4]Br, [PPN]Cl or [NBu(n)4]NCS to give [(OC)XRh(mu-p-MeC6H4NNNC6H4Me-p)2PdCl(PPh3)]- (X = I 3-, Br 4-, Cl 5- or NCS 6-) and [NBu(n)4][(OC)XRh(mu-p-MeC6H4NNNC6H4Me-p)2Pd(eta(3)-C3H5)], (X = I 7- or Br 8-). The allyl complexes 7- and 8- undergo one-electron oxidation to the corresponding unstable neutral complexes 7 and 8 but, in the presence of the appropriate halide, oxidative substitution results in the stable paramagnetic complexes [NBu(n)4][X2Rh(mu-p-MeC6H4NNNC6H4Me-p)2Pd(eta(3)-C3H5)], (X = I 9- or Br 10-). X-Ray structural (9-), DFT and EPR spectroscopic studies are consistent with the unpaired electron of 9- and 10- localised primarily on the Rh(II) centre of the [RhPd]4+ core, which is susceptible to oxygen coordination at low temperature to give Rh(III)-bound superoxide.     

Mononuclear gold(I) acetylide complexes with urea group: synthesis, characterization, photophysics, and anion sensing properties

A series of mononuclear gold(I) acetylide complexes with urea moiety, R'(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(4)-4-R (R' = cyclohexyl, R = NO(2) (2a), CF(3) (2b), Cl (2c), H (2d), CH(3) (2e), (t)Bu (2f), OCH(3) (2g); R' = phenyl, R = NO(2) (3a), OCH(3) (3b); R' = 4-methoxyphenyl, R = H (4a), OCH(3) (4b)), have been synthesized and characterized. The crystal structures of Ph(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(4)-4-NO(2) (3a) and (4-CH(3)OC(6)H(4))(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(5) (4a) have been determined by X-ray diffraction. Complexes 2a-2g, 3b, and 4a-4b show intense luminescence both in the solid state and in degassed THF solution at 298 K. Anion binding properties of complexes 2a-2g, 3a-3b, and 4a-4b have been studied by UV-vis and (1)H NMR titration experiments. In general, the log K values of 2a-2g with the same anion in THF depend on the substituent R on the acetylide ligand of 2a-2g: R = NO(2) (2a) > CF(3) (2b) ≥ Cl (2c) > H (2d) > CH(3) (2e) ≈ (t)Bu (2f) ≥ OCH(3) (2g). Complex 2a with NO(2) group shows the dramatic color change toward F(-) in DMSO, which provides an access of naked eye detection of F(-).     

Al and Zn complexes bearing N,N,N-tridentate quinolinyl anilido-imine ligands: synthesis, characterization and catalysis in l-lactide polymerization

Reactions of N,N,N-tridentate quinolinyl anilido-imine ligands with AlMe(3) afford mononuclear aluminum complexes {κ(3)-[{2-[ArN[double bond, length as m-dash]C(H)]C(6)H(4)}N(8-C(9)H(6)N)]}AlMe(2) (Ar = 2,6-Me(2)C(6)H(3) (1a), 2,6-Et(2)C(6)H(3) (1b), 2,6-(i)Pr(2)C(6)H(3) (1c)) or dinuclear complexes AlMe(3){κ(1)-[{2-[ArN[double bond, length as m-dash]C(H)C(6)H(4)]N(8-C(9)H(6)N)}-κ(2)]AlMe(2) (R = 2,6-Me(2)C(6)H(3) (2a), 2,6-Et(2)C(6)H(3) (2b), 2,6-(i)Pr(2)C(6)H(3) (2c)) depending on the ratios of reactants used. Similar reactions of ZnEt(2) with these ligands give the monoligated ethyl zinc complexes {κ(3)-[{2-[ArN[double bond, length as m-dash]C(H)]C(6)H(4)}N(8-C(9)H(6)N)]}ZnEt (Ar = 2,6-Me(2)C(6)H(3) (3a), 2,6-Et(2)C(6)H(3) (3b), 2,6-(i)Pr(2)C(6)H(3) (3c)) or bisligated complexes {κ(3)-[{2-[ArN[double bond, length as m-dash]C(H)]C(6)H(4)}N(8-C(9)H(6)N)]}Zn{κ(2)-[{2-[ArN[double bond, length as m-dash]C(H)]C(6)H(4)}N(8-C(9)H(6)N)]} (Ar = 2,6-Me(2)C(6)H(3) (4a), 2,6-Et(2)C(6)H(3) (4b), 2,6-(i)Pr(2)C(6)H(3) (4c)). These complexes were well characterized by NMR and the structures of 1a, 2a, 2c, 3b and 4c were confirmed by X-ray diffraction analysis. The aluminum and zinc complexes were tested to initiate lactide polymerization in which the zinc complexes show moderate to high activities in the presence of benzyl alcohol.     

Laser ablation generation of cluster ions from concentrated sulfuric and selenic acids

The generation and identification of novel homo- and hetero-polyacid clusters was achieved using a standard matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometer. The formation of several singly charged species was achieved via the interaction of a laser beam with concentrated sulfuric acid, selenic acid or their mixtures, applied on a graphite microcrucible. A higher yield of the species was observed in the negative detection mode, where sulfuric acid adducts HSO(4) (-) . mH(2)SO(4) (m = 0-3) and HSO(4) (-) . mH(2)SO(4) . SO(3) (m = 1, 2), and selenic acid adducts HSeO(4) (-), HSeO(4) (-) . X (X = SeO(3), H(2)SeO(4), 2SeO(3), H(2)SO(4) . SeO(3)) and NaSeO(4) (-). Y (Y = H(2)SeO(4), H(2)SeO(4). SeO(3), 2H(2)SO(4), H(2)SeO(4) . 2SeO(3), 2H(2)SeO(4) . SeO(3), 3H(2)SeO(4)), were identified. In the mass spectra of the mixture of acids, besides the homo-polyacidic adducts, eleven mixed species containing both sulfuric and selenic acid molecules or ions were identified, of which the heaviest was found to correspond to NaSeO(4) (-) . H(2)SeO(4) . 3SO(3). The stoichiometry of the species was confirmed using isotopic pattern modeling.     

Quantum Chemistry Study on the Geometrical Structures of Small Centipedo－boranes

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Structures and magnetic properties of an antiferromagnetically coupled polymeric copper(II) complex and ferromagnetically coupled hexanuclear nickel(II) clusters

Reactions between 2,6-diformyl-4-methylphenol (DFMF) and tris(hydroxymethyl) aminomethane (THMAM = H(3)L2) in the presence of copper(II) salts, CuX(2) (X = CH(3)CO(2)(-), BF(4)(-), ClO(4)(-), Cl(-), NO(3)(-)) and Ni(CH(3)CO(2))(2) or Ni(ClO(4))(2)/NaC(6)H(5)CO(2), sodium azide (NaN(3)), and triethylamine (TEA), in one pot self-assemble giving a coordination polymer consisting of repeating pentanuclear copper(II) clusters {[Cu(2)(H(5)L(2-))(μ-N(3))](2)[Cu(N(3))(4)]·2CH(3)OH}(n) (1) and hexanuclear Ni(II) complexes [Ni(6)(H(3)L1(-))(2)(HL2(2-))(2)(μ-N(3))(4)(CH(3)CO(2))(2)]·6C(3)H(7)NO·C(2)H(5)OH (2) and [Ni(6)(H(3)L1(-))(2)(HL2(2-))(2)(μ-N(3))(4)(C(6)H(5)CO(2))(2)]·3C(3)H(7)NO·3H(2)O·CH(3)OH (3). In 1, H(5)L(2-) and in 2 and 3 H(3)L1(-) and HL2(2-) represent doubly deprotonated, singly deprotonated, and doubly deprotonated Schiff-base ligands H(7)L and H(4)L1 and a tripodal ligand H(3)L2, respectively. 1 has a novel double-stranded ladder-like structure in which [Cu(N(3))(4)](2-) anions link single chains comprised of dinuclear cationic subunits [Cu(2)(H(5)L(2-))(μ-N(3))](+), forming a 3D structure of interconnected ladders through H bonding. Nickel(II) clusters 2 and 3 have very similar neutral hexanuclear cores in which six nickel(II) ions are bonded to two H(4)L1, two H(3)L2, four μ-azido, and two μ-CH(3)CO(2)(-)/μ-C(6)H(5)CO(2)(-) ligands. In each structure two terminal dinickel (Ni(2)) units are connected to the central dinickel unit through four doubly bridging end-on (EO) μ-azido and four triply bridging μ(3)-methoxy bridges organizing into hexanuclear units. In each terminal dinuclear unit two nickel centers are bridged through one μ-phenolate oxygen from H(3)L1(-), one μ(3)-methoxy oxygen from HL2(2-), and one μ-CH(3)CO(2)(-) (2)/μ-C(6)H(5)CO(2)(-) (3) ion. Bulk magnetization measurements on 1 show moderately strong antiferromagnetic coupling within the [Cu(2)] building block (J(1) = -113.5 cm(-1)). Bulk magnetization measurements on 2 and 3 demonstrate that the magnetic interactions are completely dominated by ferromagnetic coupling occurring between Ni(II) ions for all bridges with coupling constants (J(1), J(2), and J(3)) ranging from 2.10 to 14.56 cm(-1) (in the ? = -J(1)(?(1)?(2)) - J(1)(?(2)?(3)) - J(2)(?(3)?(4)) - J(1)(?(4)?(5)) - J(1)(?(5)?(6)) - J(2)(?(1)?(6)) - J(3)(?(2)?(6)) - J(3)(?(2)?(5)) - J(3)(?(3)?(5)) convention).     

Synthesis and pharmacological evaluation of some 3-(4-methoxyphenyl)-2-substitutedamino-quinazolin-4(3H)-ones as analgesic and anti-inflammatory agents

A variety of novel 3-(4-methoxyphenyl)-2-substitutedamino-quinazolin-4(3H)-ones were synthesized by reacting the amino group of 2-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one with a variety of alkyl and aryl ketones. The starting material 2-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one was synthesized from 4-methoxyaniline. The title compounds were investigated for analgesic, anti-inflammatory and ulcerogenic index activities. While the test compounds exhibited significant activity, compounds 2-(1-methylpropylidene)-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one (A1), 2-(1-ethylpropylidene)-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one (A2) and 2-(1-methylbutylidene)-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one (A3) showed moderately more potent analgesic activity and the compound 2-(1-methylbutylidene)-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one (A3) showed moderately more potent anti-inflammatory activity when compared to the reference standard diclofenac sodium. Interestingly the test compounds showed only mild ulcerogenic potential when compared to aspirin.     

Synthesis and structure of tetranuclear orthometallated Pd(II) complexes derived from bis-iminophosphoranes

The reaction of Pd(OAc)2 with bis-iminophosphoranes Ph3P=NCH2CH2CH2N=PPh3 (1a), [C6H4(C(O)N=PPh3)2-1,3] (1b) and [C6H4(C(O)N=PPh3)2-1,2] (1c), gives the orthopalladated tetranuclear complexes [{Pd(mu-Cl){C6H4(PPh2=NCH2-kappa-C,N)-2}}2CH2]2 (2a) [{Pd(mu-OAc){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',3']2 (2b) and [{Pd(mu-OAc){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',2']2 (2c). The reaction takes place in CH2Cl2 for 1a, but must be performed in glacial acetic acid for 1b and 1c. The process implies in all cases the activation of a C-H bond on a Ph ring of the phosphonium group, with concomitant formation of endo complexes. This is the expected behaviour for 1a, but for 1b and 1c reverses the exo orientation observed in other ketostabilized iminophosphoranes. The influence of the solvent in the orientation of the reaction is discussed. The dinuclear acetylacetonate complexes [{Pd(acac-O,O'){C6H4(PPh2=NCH2-kappa-C,N)-2}}2CH2] (3a), [{Pd(acac-O,O'){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',3'] (3b) and [{Pd(acac-O,O'){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',2'] (3c) have been obtained from the halide-bridging tetranuclear derivatives. The X-ray crystal structure of [3c.4CHCl3] is also reported.     

Hybrid organic-inorganic 1D and 2D frameworks with epsilon-Keggin polyoxomolybdates as building blocks

Organic-inorganic hybrid materials based on polyoxometalate building blocks with capping La3+ ions and bidentate oxygenated ligands have been obtained by reaction at room temperature of the [epsilon-PMo12O36(OH)4[La(H2O)4]]5+ polyoxocation with glutarate (C5H6O(2)(2-)) and squarate (C4O(4)(2-)) organic ligands. [epsilon-PMo12O37(OH)3[La(H2O)4(C5H6O4)0.5]4].21 H2O (1) and [epsilon-PMo12O39(OH)[La(H2O)6]2-[La(H2O)5(C4O4)0.5]2].17 H2O (2) form unprecedented 1D chains built from alternating polyoxocations and organic ligands connected through LaO links. The structures of these materials are compared to the 2D hybrid organic-inorganic framework [NC4H12]2-[Mo22O52(OH)18[La(H2O)4]2[La(CH3CO2)2]4].8H2O (3) isolated from the hydrothermal reaction of elemental precursors (MoO(4)(2-), Mo, La3+) in acetate buffer. Compound 3 is built from previously undescribed polyoxometalate units with twenty-two MoV centers capped by six La3+ ions, four of which are bridged by acetate ligands.