Interactions with ATP, DNA Cleavage and Anti-tumor Activities of Complexes with Anions [Mo（V）O2（O2CeH4）2]^3-, [Mo（Ⅴ）0.5W（Ⅵ）0.5O2（O2C6H4）2]^2.5- and [W（Ⅵ）O2（O2C6H4）2]^2-

(NH3CH2CH2NH2)3[Mo(Ⅴ)O2(O2C6H4)2] (1), (NH3CH2CH2NH2)2.5[Mo(Ⅴ)o.sW(Ⅵ)o.502(O2C6H4)2] (2) and(NH3CH2CH2NH2)2[VC(Ⅵ)O2(O2C6H4)2] (3) were synthesized, structurally characterized by X-ray diffraction analysis, and studied on their interactions with ATP, their DNA cleavage activities and antitumor properties. The redox state of molybdenum was not changed on going from crystal to aqueous solutions in complexes 1 and 2, while tungsten underwent reduction from W(VI) to W(V) in complexes 2 and 3. ATP promoted the oxidation of both molybdenum and tungsten from M(Ⅴ) to M(Ⅵ) and the hydrolysis of catecholate ligands in solution consisting of ATP and the complexes. Complex 1 possesses fairly good activity to DNA cleavage and against tumor S180 in mice, and is more effective than the control drug cyclophosphamide under the identical conditions. However, complexes 2 and 3 exhibited marginal effectiveness. The effectiveness of anti-tumor of the complexes was related positively to their DNA cleavage activities and their hydrolysis of catecholate ligands.     

Synthesis and Structure of Dimolybdenum Carbonyl Thiolate Compound [Et4N]2[Mo2（CO）8（SC6H4—CH3—m）2]

1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t…     

Synthesis and Crystal Structure of Cubane—typeMolybdenum Cluster ComplexMo4S4（DTP）4[μ—SOP（OEt）2]2

1 INTRODUCTION Trinuclear molybdenum complexes with Mo3(3-S)(-O)n(-S)3n (n = 0~3) cores have been extensively studied on their diversified reactions towards various organic ligands and many metals. Many derivatives with Mo3S4 core have been rationally synthesized from the cation precursor [Mo3S4(H2O)9]4+ and its neutral derivative Mo3(3-S)(-S)3(DTP)4(H2O)[1]. However, due to their structural lability, complexes with Mo3(3-S)(-O)n(-S)3n (n = 1~3) cores have been reported limitedl…     

Synthesis,Crystal Structure of Cis—dioxo—catecholatotungsten（VI） Complex and Its NMR Studies on the Interaction with ATP

Cis-dioxo-catecholatotungsten(VI) complex anion[W^(VI)O2-(OC6H4O)2]^2- was obtained with discrete protonated ethylenediamine (NH2CH2CH2NH3)^ cations by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH3OH,CH3CN and ethylenediamine,and compared with its molybdenum anaogue [Mo^(V) O2(OC6H4O)2]^3- by crystal structure,UV,EPR,The results of the UV and EPR spectra show that tungsten is less redox active than molybdenum since the molybdenum is reduced from Mo(VI) to Mo(V) but tungsten stays in the original highest oxidized state Mo(VI) when they are crystallized from the solution above.It is worthy to note that [W^(VI)O2(OC6H4O)]^2- shows the same coordination structure as its molybdenum analogue in which the metal center exhibits distorted octahedral coordination geometry with two cis-dioxocatecholate ligands and might have the related coordination structure feature with the cofactor of flavoenzyme because [Mo^(V)O2(OC6H4O)2]^3- presented essentially the same EPR spectra as flavoenzyme.The NMR studies on the interaction of the title complex with ATP reveal that the reduction of W(VI) to W(V) occurs when the title complex is dissolved in D2O and the W(V) is oxidized again when ATP solution is mixed with original solution and the hydrolysis of the catecholato ligand take places at mean time being monitored by ^1H NMR and ^13C NMR spectra.     

Synthesis and Characterization of syn-[(η~5-C_5Me_5)_2W_2(S)_2(μ-S)_2].0.5anti-[(η~5-C_5Me_5)_2W_2(S)_2(μ-S)_2]

1 INTRODUCTION The complexes of syn- or anti-[(5-C5Me5)2- W2(S)2(-S)2] could be prepared in several ways[1~5]. For example, a mixture consisting of [Et3NH][(5-C5Me5)WS3] and anti-[(5-C5Me5)2- W2(S)2(-S)2] was generated from the reactions of [(5-C5Me5)WCl4] with H2S in the presence of NEt3[2]. The reactions of [(5-C5Me5)W(NO)I2] with H2S led a mixture of [(5-C5Me5)W(S)(S2)I] and anti-[(5-C5Me5)2W2(S)2(-S)2][3]. [(5-C5Me5)W- (StBu)3] was degraded in THF at room temperat…     

Crystal Structure of 2—[（P,P—Diphenoxy）phosphono（p—methyl）benzyl]—1,2—

The crystal structure of the title compound 2-[(P, P-Diphenoxy)phosphono(p-methyl)benzyl]-1, 2-benzisoselenazol-3(2H)-one, C27H22NO4PSe, was determined by single crystal X-ray diffraction. It crystallizes in the triclinic system, space group P(No. 2) with Mr=534.41, a=9.761(2), b=10.304(2), c=13.396(3), α=110.97(3), β=107.70(3). γ=90.02(3)°, V=1190(1) 3, Z=2, Dx=1.492 g/cm3, λ=0.71073, μ=1.6596 mm-1 and F(000)=544. The structure was solved by direct methods. The final R factor is 0.068 and Rw is 0.074 for 2500 unique observed reflections [I≥3σ(I)]. The results presented herein indicate that the selenium-containing bicyclic moiety is a coplanar structure and that two adjacent molecules are symmetrically linked to each other forming a dimer through the Se(1c)...O=P(1) bonding interaction with an intermolecular Se(1c)...O distance of 2.797 .     

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 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.     

Cleavage of the Fe—Fe Bond of （Me2SiSiMe2） [η^5－C5H4Fe（CO）2]2 with Na／Hg and Molecular Structure of the Ring－Opened Complex

The reaction of the rifle cyclic complex (1) with sodium amalgam in THF resulted in the expected cleavage of the Fe-Fe bond to afford his-sodium salt ( Me2SiSiMe2 ) [η^5-C5H4Fe(CO)2]2 (4). The latter was not isolated and was used directly to react with MeI, PhCH2Cl, CH3C(O)Cl, PhC(O)Cl,Cy3SnCl (Cy= cyclohexyl) or Ph3SnCl to afford corresponding ring-opened derivatives (Me2SiSiMe2) [η^5-C5H4Fe(CO)2]2 [5, R=Me; 6, R=PhCH2; 7, R=CH3C(O); 8, R=PhC(O); 9, R = Cy3Sn or 10, R = Ph3Sn ]. The crystal and molecular structures of 10 were determined by X-ray diffraction analysis. The molecule took the desired ant/ conformation around the Si-Si bond. The length of the Si--Si bond is 0.2343(3)nm, which is essentially identical to that in the cyclic structure of 1[0.2346(4) tun]. This result unambiguously demonstrates that the Si--Si bond in the cyclic structure of 1 is not subject to obvious strain.     

Synthesis and Structure of [Cu2（μ—NO2）（aepy）4]（ClO4）3 （aepy=2—（2—Aminoethyl）pyridine）

1 INTRODUCTION There has been great and considerable interest in the study of copper nitrite complexes because they are relevant to the study of copper-containing enzymes involved in the denitrification process[1]; in particular, copper-nitrite complexes are potentially relevant to the nitrite reductases[2] (the enzyme from Achromobacter Cycloclastes) which convert NO2－ to NO and/or N2O. Many attempts have been made to synthesize a variety of copper-nitrite complexes, in which the n…     

Synthesis and Crystal Structure of a Molybdenum Carbonyl Compound with Thiolate and Dithiocarbamate Ligands, [Bu4N][（OC）4Mo（μ-SC6H5）2Mo（C5H10CNS2）（CO）2]

1INTRODUCTION The chemistry of molybdenum-sulfur compounds has attracted the attention from chemists,bioinor-ganic chemists and biochemists because Mo and S are important elements of metal enzymes especially N2-ase[1~6].Since the di-molybdenum(0)thiolate com-pound with a[Mo2S2]2?unit core and two-electron transfer character,[Et4N]2[Mo2(SR)2(CO)8](R=Ph,tBu),was synthesized by introducing thiolate ligands into Mo(CO)6[7],the chemistry of complexes conta-ining low valence molybdenum at…     

Crystal Structure of cis—2—[P,P—Diethoxy） phosphono（m—nitro）benzyloxy]

The crystal structure of the title compound cis-2-[(P, P-Diethoxy)phosphono(m-nitro)benzyloxy]-4-Phenyl-5,5-Dimethyl-1,3,2-Dioxaphosphorinane 2-Sulfide, C22H29NO8P2S, was determined by single crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c, with Mr=529.49, a=9.888(2), b=20.831(4), c=12.797(3) , β=94.42(3)°, V=2628(1) 3, Z=4, Dx=1.338 g/cm3, λ=0.71073, μ=0.2796 mm-1 and F(000)=556. The structure was solved by direct methods. The final R factor is 0.052 and Rw is 0.057 for 1793 unique observed reflections [I≥3σ(I)]. A cis-configuration and a preferred chair conformation for the molecule have been established by X-ray diffraction analysis. The results presented also give a good explanation to the correlation between the configurational assignments and the regularity in the chemical shifts of C4-H and 31P NMR.     

Synthesis and Crystal Structure of a Novel Polymeric Complex [WS4Cu4（PY）4（μ-CN）2]∞

1 INTRODUCTION The synthesis of Mo(W)/Cu(Ag,Tl)/S polymeric complexes from the reactions of [MS4]2- (M = Mo, W) with Cu , Ag or Tl remains attractive due to their rich coordination chemistry[1～10] and NLO ma- terials[7, 10]. For example, the reacti…     

Crystal Structure of Chiral Acetato-bridged Binuclear Cyclopalladated complex[Pd（μ-O2CM3）（S-C6H4CHMeNH2）]2

Reaction of (S)-α-methylbenzylamine with Pd(OAc)2 in anhydrous HOAc produced the chiral complex[Pd(μ-O2CMe)(S-C6H4CHMeNH2)]2.(1).The complex was characterized by 1H NMR spectroscopy,elemental analysis and a single-crystal Xray analysis.The X-ray crystal structure analysis revealed that complex 1 has four isomers:two outer and two inner isomers.     

Synthesis and Structure Characterization of Mn2（CO）6（μ—S2CP^iPr3）

1INTRODUCTIONThechemistryofhomobinuclearcomplexeshasbeenaveryactivefieldofresearchinthepastdecadesbecauseoftheirnovelstructuresandapplicationsinorganicsynthesis[1,2].Atthesametimephosphine-carbondisulfideadducts,S2CPR3,areveryversatileligandswithavarietyofcoo-rdinationmodestotransitionmetalcenters.Itisabletoformallydonatefrom2to8etoametalormetals[3].AlthoughMn2(CO)6(m-S2CPiPr3)hasbeensynthesizedbyMiguelD.etal.[4,5],nocrystallo-graphicdatatillnowareavailableforit.Inthispaperwewilldesc…     

Study on the Stereoselective Synthesis of Carbapenem Sidechain （2S,4S）-4-Acetylsulphanyl-2- [（S）-l-phenylethylcarbamoyl]- pyrrolidine-l-carboxylic Acid 4-Nitrobenzyl Ester

A stereoselective and economic synthesis of the carbapenem sidechain (2S, 4S)-4-ace-tylsulphanyl-2- [ (S) 1-phenylethyl-carbamoyl] pyrrolidine-l-carboxylic acid 4-nitrobenzyl ester was developed. Due to the effect of spatial hindrance, only the (2S,4S) diastereomer 3 was obtained by coupling 1 and the inexpensive racemic 2 catalyzed by EEDQ.     

Spectroscopic study on the interaction between[Hg（SCN）4]2- and hemoglobin

The interaction between[Hg（SCN）₄]^2- and hemoglobin（Hb） under conditions that simulate a physiological environment was investigated by UV-vis spectroscopy,fluorescence spectroscopy,resonance Rayleigh scattering（RRS） spectroscopy and circular dichroism（CD） spectroscopy.The results obtained from the change of UV-vis and CD spectra,the quenching of Hb fluorescence and the enhancement of RRS intensity proved that a 10:1 type complex was formed between[Hg（SCN）₄]^2- and Hb.The possible mechanism suggested for the interaction was that ten Hg（SCN）₄]^2- anions entered the four subunits of a Hb molecule to react with some residues to form an adduct by coordination and electrostatic forces.The coordination of[Hg（SCN）₄]^2- with Trp was the major cause of the fluorescence quenching of Hb.     

Towards Single-component Molecular Conductor [Ni（dmit）2 ] by Charge Disproportionation： 2[Ni（dmit）2]^0.5→[Ni（dmit）2 ]＋ [Ni（dmit）2]^-

A new method of synthesizing single-component molecular conductor [Ni(dmit)2] bythe reaction 2(Me4N)[Ni(dmit)2]2→ [Ni(dmit)2] (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2]exhibits a semiconductive behavior above 167 K, while from 167 K down to the measuring limit of 60 K, it exhibits metallic conductivity.     

Synthesis and Crystal Structures of Three Ladder Distannoxane Dimers [（PhCH2）2（Cl）SnOSn（X）（CH2Ph）2]2（X=Cl,OMe,OEt）

Three distannoxane dimers[(PhCH2)2(Cl)SnOSn(X)(CH2Ph)2]2(X=Cl,OMe,OEt)were prepared by the hydrolytic reaction of (PhCH2)2SnCl2 with sodium alkoxides.The compounds are assigned tetranuclear distannoxane structures in solid state.which contain the so-called ladder arrangement with a central planar Sn2O2 four-membered ring.The endo-and exo-cyclic Sn atoms are both five-coordinate,and have distorted trigonal bipyramidal geometries.A variety of hydrolyses of(PhCH2)2SnCl2 were performed and these dimers were characterized by IR,^1H NMR spectroscopy and X-ray diffraction analysis.     

Construction of J-and H-Aggregates of meso-Tetrakis （4-hydroxyphenyl） porphyrin Diacid （H4THPP^2＋）

UV-Vis spectrum was utilized to study the aggregation behaviors of H4THPP^2 in DMF-chloroform mixture and water. It was found that J-aggregation of H4THPP^2 was formed in DMF-chloroform mixture and H-aggregate was formed in aqueous solution with high ionic-strength, as indicated by different spectral characteristics of different H4THPP^2 aggregates.