Structure of 〔Na(DB18C6) (CH_3OH)〕_2W_6O_(19)·(DB18C6)·(CH_3OH)

1INrnODUCTIoNlnthepreviouspapers,wehavereportedthesynthesisandcrystalstructureofseveralcrownetherpolyoxometalates"-",nowwestudythestructureofthetitlecomplexandcompareitwithsomeothercrownetherpolyoxometalatecomplexes.2EXPERmENTALToal5OmLaqueoussolutioncontaining32g(1OOmol)Na,WO#.2H,Opre-justedtopH=3.5withchloricacid,14g(4Ommol)(n-Bu)'NBrwasadded,thenwhitepowderwasformed.ThewhiteprecipitateobtainedwithafiltrationwaskeptasthenewmaterialAinnextstep.AmixtureoflgAandO.3g(O.8mmol)DB18…     

CRYSTAL STRUCTURE OF (NH_4)_(11)[Na(H_2O)_2P_4W_(14)O_(58)] ·12H_2O

<正> (NH4)11[Na(H2O)2P4W14O58)·12H2O, Mr = 4099. 39, triclinic, space group P1, a = 14. 376(2), b = 19.861(9), c=13. 010(3)(?) , α=104. 68(2), β=91. 37(1), γ= 104. 05(2)°, V = 3471. 1 (?)3, Z = 2, Dc=3. 922g/cm3, μ (MoKα) = 238. 274cm-1, F(000) = 3664, R = 0.0510, Rw = 0. 0665 for 9260 observed reflections with I> 3σ(I). The polyanion [Na(H2O)2P4W14O58]11- consists of two PW7O29 subunits anisostructurally, two linkage phosphorous atoms and one sodium ion with two water ligands as well. The geometries of tungsten atoms within these two subunits are almost the same as those in K12P4W14O58· 21H2O[2]. The four phosphorous atoms are in PO4 coordinations. The sodium ion locates nearly at the center of the polyanion, and is coordinated by two water molecules, five oxygen atoms of the anion and one phosphorous atom with Na-P = 3. 053(3) (?). Due to the presence of the sodium atom, the interactions between oxygen and tungsten atoms in the polyanion are somewhat weakened.     

含有环己巯基配体的钨簇合物的合成及晶体结构研究

C6H11Na, Et4NBF4, FeCl2, (NH4)2WS4在20mL CH3OH溶剂的反应中, 标题簇合物(Et4N)3[W2Fe6S8(SC6H11)6(OCH3)3]被分离得到, 对其进行X-ray 单晶衍射和结构解析。 该化合物属正交晶系,空间群 Pmmn, 晶胞参数 a = 17.370(5), b = 15.986(4), c = 17.858(3), V = 4958.6(6)3, Z = 2,C63H135N3O3S14Fe6W2, Mr = 2134.47, Dc = 1.43g/cm3, F(000) = 2172.0, m(MoKa) = 3.49 mm-1, T = 293(2)K。 采用2966个I > 2.0s (I) 的衍射点对所有非氢原子参数进行结构修正。 得到最后的偏离因子为R = 0.072, Rw = 0.091。 这是一个双类立方烷的结构, 2个单类立方烷的端基金属钨原子通过3个甲氧基桥联。 [WFe3S4] 与 [MoFe3S4]簇核结构比较说明, 两者存在一定的相似性。     

Synthesis and Characterization of a New Pure Inorganic 2D Network Based on [H_2W_（12）O_（42）]~（10-）

An isopolytungstate(NH4)6Na4[H2W12O42]·14H2O(1) has been synthesized in an aqueous solution and characterized by elemental analysis,IR spectroscopy,TG analysis,X-ray powder diffraction(XRD) and single-crystal X-ray diffraction.The result indicates a degradation from nitrilotriacetic acid(NTA) to NH3.The electrochemical analysis and thermal stability of 1 were also studied.The crystal data are as follows:H54N6Na4O56W12(Mr = 3332.65),orthorhombic,Pbca,a = 14.1497(15),b = 15.9414(16),c = 22.931(2) ,Z = 4,V = 5172.4(9) 3,Dc = 4.280 Mg/m3,μ = 26.729 mm-1,F(000) = 5904,the final R = 0.0809 and wR = 0.2104 for 4565(Rint = 0.1351) independent reflections.The β-[H2W12O42]10-clusters are linked through {Na2(OH2)3} groups into a 2D layer and are further connected into a 3D framework via hydrogen bonding interactions.     

Syntheses and spectroscopic and structural characterization of molybdenum(VI) citrato monomeric raceme and dimer, K4[MoO3(cit)].2H2O and K4[(MoO2)2O(Hcit)2].4H2O

Investigation of the aqueous coordination chemistry for citrate and molybdenum(VI) resulted in the isolation of molybdenum(VI) citrato monomeric raceme and dimer K4[MoO3(cit)].2H2O (1) and K4[(MoO2)2O(Hcit)2].4H2O (2) (H4cit = citric acid). Complex 1 can serve as the first structurally characterized monomeric citrato molybdate and may represent an early mobilized precursor in the biosynthesis of FeMo-co (FeMo-cofactor). The two complexes have been characterized by elemental analyses and IR and NMR spectroscopies. The IR and NMR spectra are consistent with a monomeric species or a monooxo-bridged dinuclear structure, as revealed by a single crystal X-ray diffraction study. Compound 1 is monoclinic space group P2(1)/c with a = 7.225(1) A, b = 9.151(2) A, c = 22.727(2) A, beta = 94.93(1) degrees, V = 1497.1(7) A3, and Z = 4. Full-matrix least-squares refinement resulted in residuals of R = 0.027 and Rw = 0.032. The molybdenum atom forms an octahedral coordination with three oxo groups and one tridentate citrate, in which the latter is coordinated through the alkoxy and vicinal carboxyl and much more weakly by one of the two terminal groups [2.411(3) A]. Compound 2 is triclinic space group P1 with a = 8.2728(8) A, b = 8.9514(8) A, c = 10.0605(9) A, alpha = 101.673(8) degrees, beta = 100.672(7) degrees, gamma = 112.938(7) degrees, V = 642.5(3) A3, and Z = 1. Full-matrix least-squares refinement resulted in residuals of R = 0.033 and Rw = 0.039. The complex anion contains a linear (O2Mo)O(MoO2) core with the bridging oxo group lying at the center of inversion symmetry (Mo-Ob-Mo, 180 degrees). Each citrate ligand is three-coordinated to one molybdenum atom through the deprotonated hydroxy, alpha-carboxyl, and one beta-carboxyl group, making each metal atom six-coordinate.     

含柠檬酸配体的钼硫簇合物的合成与晶体结构的测定

合成了含有Mo—S簇阴离子 [Mo2 O2 ( μ S) 2 (C6H5O7) (C6H4 O7) ]5-柠檬酸簇合物 ,并通过元素分析、红外光谱、紫外 可见光谱和X射线光电子能谱对配合物进行了表征 ,用X射线衍射法测定了该化合物的晶体结构 .结果表明 ,该簇合物属于单斜晶系 ,空间群P2 1/c,a =2 3 766( 5)nm ,b =1 3 2 74 ( 3 )nm ,c =2 2 4 71 ( 5)nm ,α=γ =90°,β=1 1 8 2 1°,V =6 2 4 7( 2 )nm3 ,Z =8,一致性因子R =0 0 83 1 ,R2 ,w=0 1 536.该簇合物阴离子中每一个Mo原子都采取扭曲的八面体结构 ,柠檬酸通过羟基、α 羧基、一个 β 羧基与Mo配位 .晶体结构表明在一个结晶学上不对称的结构单元内有两个结晶学上独立的分子 .     

Isolations and characterization of highly water-soluble dimeric lanthanide citrate and malate with ethylenediaminetetraacetate

Highly water-soluble lanthanum and cerium citrates or malates with ethylenediaminetetraacetate (NH(4))(8)[Ln(2)(Hcit)(2)(EDTA)(2)]·9H(2)O [Ln = La, 1; Ce, 2], K(8)[La(2)(Hcit)(2)(EDTA)(2)]·16H(2)O (3) and K(6)[Ln(2)(Hmal)(2)(EDTA)(2)]·14H(2)O [Ln = La, 4; Ce, 5] (H(4)cit = citric acid, H(3)mal = malic acid, and H(4)EDTA = ethylenediaminetetracetic acid) were prepared from the reactions of lanthanide ethylenediaminetetraacetate trihydrates with citric or malic acid at pH 5.0-6.5. These compounds were characterized by elemental analyses, IR, TG-DTG, solution (13)C{(1)H} NMR, solid state (13)C NMR spectra and X-ray structural analyses. The main structural feature of the compounds consists of a dinuclear unit deca-coordinated by EDTA and citrate or malate. The α-hydroxy and α-carboxy groups of citrate and malate chelate in five-membered ring with one lanthanide ion, while one of the β-carboxy group coordinates with the other lanthanide ion, forming a dimeric structure. The other pendent β-carboxy groups in 1-3 form very strong intramolecular hydrogen bond with α-hydroxy groups [O1O7 2.594(4), 2.587(8) and 2.57(1) ? for 1-3 respectively]. (13)C NMR spectra of the lanthanum compounds show obvious downfield shifts based on solid and solution NMR measurements, indicating the coordinations of mixed-ligand in lanthanum complexes, while highfield shifts are observed in cerium complexes.     

An expanded set of functional groups in bis(dithiolene)tungsten(IV,VI) complexes related to the active sites of tungstoenzymes, Including WIV-SR and WVI-O(SR)

The active sites of tungstoenzymes have the formulations W(IV,V)L(S(2)pd)(2) and W(VI)LL'(S(2)pd)(2), in which two pyranopterindithiolene cofactor ligands (S(2)pd) are chelated to a tungsten atom. Ligands L and/or L' are not fully defined in any wild-type enzyme. The feasibility of various coordination fragments (functional groups) in potential bis(dithiolene)tungsten site analogues has been examined in previous work by exploratory synthesis. This investigation expands the range of accessible functional groups. The synthetic scheme originates with [W(CO)(2)(S(2)C(2)Me(2))(2)], whose carbonyl groups are labile to substitution. Complexes [W(IV,VI)LL'(S(2)C(2)Me(2))(2)](1-) are described in terms of their functional groups W(IV,VI)LL'. Reaction of the dicarbonyl with formate in acetonitrile/THF affords W(IV)(CO)(eta(1)-HCO(2)) (4) and in Me(2)SO W(VI)O(eta(1)-HCO(2)) (7) by an oxo transfer reaction. Carboxylates yield six-coordinate W(IV)(eta(2)-O(2)CR) (1-3, R = Ph, Me, Bu(t)) with C(2)(v) symmetry. Reaction of 3 (R = Bu(t)) with Me(3)SiSR (R = C(6)H(2)-2,4,6-Pr(i)(3)) gives W(IV)(SR) (5), which undergoes oxo and sulfido atom transfer to form W(VI)O(SR) (8) and W(VI)S(SR) (9), respectively. Attempts to prepare corresponding selenolate complexes, pertinent to the active site of formate dehydrogenase, were unsuccessful, including reactions of W(VI)OCl (10) with RSe(-). Structure proofs of 2-10 were obtained by X-ray structure determinations. Some 26 functional group types in bis(dithiolene)W(IV,V,VI) molecules have now been achieved by synthesis. It remains to be seen which are incorporated in an enzyme site. A number of them (e.g., 5) are directly analogous to molybdoenzyme sites, and may possess corresponding reactivity with biological substrates, as do W(IV)(OR)/W(VI)O(OR) (prepared earlier) in the reduction of N- and S-oxides by atom transfer.     

Solid and Solution Structural Studies of Dimeric and Tetrameric Molybdenum（VI） Malate Complexes

Reactions of potassium molybdate with racemic malic acid （H3mal = C4H6O5） result in the isolation of two mesomeric molybdenum malate complexes K8[（MoO2）2O（R-mal）2][（MoO2）2O（Smal）2]-4H2O 1 and （Him）2K6[（MoO2）4O3（R-mal）2][（MoOE）4O3（S-mal）2]-8H2O 2. Complex 1 belongs to the monoclinic system, space group C2/c with a = 14.8637（3）, b = 6.9544（1）, c = 19.6783（5）A, β = 100.081（2）°, V = 2002.70（7） A^3, Mr = 1452.88, Z = 2, F（000） = 1416, T = 173 K, Dc = 2.409 g/cm3, fl（MoKa＇） = 2.167, R = 0.0283 and wR = 0.0733.2 is of triclinic system, space group P1^- with a = 8.7707（2）, b = 9.3310（3）, c = 17.9093（7）A, α= 83.781（3）, β = 85.626（2）, y= 84.822（2）°, V = 1447.84（8）A^3, Mr = 2160.68, Z = 1, F（000） = 1048, T = 173 K, Dc = 2.478 g/cm^3,μ（MoKα） = 2.230, R = 0.0234 and wR = 0.0584.1 is the first isolated dinuclear molybdenum（VI） malato complex in 1：1 molar ratio. The molybdenum atoms in the two complexes are six-coordinated in an approximately octahedral geometry. Two malates coordinate tridentately with the Mo atom via their α-alkoxy, α-carboxy and α-carboxy groups in 1 and 2. β-Carboxy group in 2 further links with the other two Mo atoms to give a tetrameric unit. The solution ^1H and ^13C NMR spectra indicate that dimeric malate molybdenum in 1 dissociates partly in solution and exists in an equilibrium with tetrameric species, while 2 is stable and retains its tetrameric structure without any dissociation.     

［Vmo_3O_4（O_2CEt）_8］_2Na_2的合成与结构

［ＶＭｏ３Ｏ４（Ｏ２ＣＥｔ）８］２Ｎａ２（１），三斜晶系，Ｐ１空间群，ａ＝１２．９７７（７），ｂ＝１４．０７０（６），ｃ＝１２．３３８（８），α＝１０９．８１（４），β＝１１７．２０（４），γ＝９０．５１（５）°，Ｖ＝１８４８．８３，Ｍｒ＝２０２０．６，Ｄｃ＝１．８１ｇ／ｃｍ３，Ｚ＝１，Ｆ（０００），μ＝１２．９ｃｍ１（ＭｏＫα）对３７４２个可观测反射点（Ｉ＞３σ（Ｉ））最终一致性因子为Ｒ＝０．０１８，Ｒω＝０．０５４。单晶结构分析表明，簇阴离子中两个［Ｍｏ３Ｏ４］４＋单元通过两个＂桥＂金属Ｖ原子连接成一个奇特的环状结构，Ｍｏ－Ｍｏ平均键长为２．５１９（１），Ｍｏ…Ｖ间平均距离为３．６５４。簇阴离子通过Ｎａ＋连成一个一维长链，Ｎａ原子与氧原子形成一个少见的五配位三角双锥结构，Ｎａ－Ｏ距离仅为２．３１２，Ｎａ－Ｏ间较强的相互作用以及无限长链的晶体结构很好地解释了簇合物（１）的稳定性和不溶性。     

Dioxotungsten 1,2-benzenedithiolate complex stabilized by NH...S hydrogen bonds

Novel dioxo-tungsten(VI) bis(1,2-benzenedithiolate) complexes with neighboring amide groups, as models for tungsten enzymes, (NEt4)2[W(VI)O2{1,2-S(2)-3,6-(RCONH)2C6H2}2] (R = CH3, t-Bu), were designed and synthesized. The presence of the NH...S hydrogen bond was confirmed through IR spectrometry and X-ray crystallographic analysis. In the W(VI)O2 complexes, the NH...S hydrogen bond trans to the oxo ligand is stronger than that cis to oxo. On the basis of comparisons with [W(VI)O2(1,2-S2C6H4)2](2-), the NH...S hydrogen bond positively shifted the W(VI)/W(V) redox potentials and depressed the reduction by benzoin or triphenylphosphine. These results suggest that the NH...S hydrogen bond stabilizes the oxo ligand through trans influence and regulates O-atom transfer in tungsten and molybdenum enzymes.     

CRYSTAL AND MOLECULAR STRUCTURE OF BIS(2-ME-THOXYETHYL-CYCLOPENTADIENYL) ERBIUM CHLORIDE

<正> Complex Cp'2 ErCl(Cp'=2-methoxyethylcyelopentadienyl)(I)has been synthesized by the reaction of Cp' Na and ErCl3 in THF It crystallizes in space group Pnma with a=12.269(0),b=11.742(6),c=11.197(2)A,V=1613.1A3,Dc=1.849 g/cm3,Z=4,A=0.71073 A,μ(MoKa)=54.38 cm-1,F(000)=876,R=0.043,Rw=0.046.The Er atom is formally nine-coordinated with a pseudo-trigonal bipyramidal geometry with the "equatorial" plane composed of the Er atom,the Cl atom and the centers(1)and(2)of the two Cp rings(Cp=cy-clopentadienyl).The molecule is located at the crystallographic mirror plane through the atom C(3),C(4),C(S),Er,O(1)and C(6).The atom Cl and the atoms of Cp'(2)(except C(16)and C(16'))are disordered with an occupancy of 0.5 each.     

Complexation of Molybdenum（Ⅵ） with R－and S－malic Acid， The Crystal Structure of（NH_4）_4［（MoO_2）_4O_3（R－mal）_2］·6H_2O

ＣｏｍｐｌｅｘａｔｉｏｎｏｆＭｏｌｙｂｄｅｎｕｍ（Ⅵ）ｗｉｔｈＲ－ａｎｄＳ－ｍａｌｉｃＡｃｉｄ，ＴｈｅＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ（ＮＨ_４）_４［（ＭｏＯ_２）_４Ｏ_３（Ｒ－ｍａｌ）_２］·６Ｈ_２ＯＺｈｏｕＺｈａｏ－Ｈｕｉ；ＹａｎＷｅｎ－Ｂｉ?..     

Synthesis, characterization, and electrochemistry of cis-oxothio- and cis-bis(thio)tungsten(VI) complexes of hydrotris(3,5-dimethylpyrazol-1-yl)borate

The complexes TpWO2X react with sulfiding agents such as B2S3 or P4S10 to give the oxothio- and bis(thio)tungsten(VI) complexes TpWOSX (X = Cl(-)) and TpWS2X [X = Cl(-), S2PPh2(-); Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate]. The reaction of TpWS2Cl with (i) PPh3 in pyridine and (ii) dimethyl sulfoxide affords TpWOSCl in good overall yield. The chloro complexes undergo metathesis with alkali metal salts to yield species of the type TpWOSX and TpWS2X [X = OPh(-), SPh(-), SePh(-), (-)-mentholate]. The diamagnetic complexes exhibit NMR spectra indicative of C(1) (TpWOSX) or C(s) (TpWS2X) symmetry and IR spectra consistent with terminal oxo and thio ligation (nu(W=O), 940-925 cm(-1); nu(W=S) or nu(WS2), 495-475 cm(-1)). Crystals of (R,S)-TpWOS[(-)-mentholate] are monoclinic, space group P2(1), with a = 11.983(2) A, b = 18.100(3) A, c = 13.859(3) A, beta = 91.60(2) degrees, V = 3004.6(8) A(3), and Z = 4. Crystals of TpWS2(OPh)-CH2Cl2 are orthorhombic, space group Pbca, with a = 16.961(4) A, b = 33.098(7) A, c = 9.555(2) A, V = 5364(2) A(3), and Z = 8. The mononuclear, distorted-octahedral tungsten centers are coordinated by a tridentate Tp ligand, an alkoxy or aryloxy ligand, and two terminal chalcogenide ligands. The average W=O and W=S distances are 1.726(7) and 2.125(2) A, respectively, and the O=W=S and S=W=S angles 102.9(3) and 102.9(1) degrees, respectively. The tungsten and sulfur X-ray absorption spectra of TpWOSCl and TpWS2Cl are consistent with the presence of terminal pi-bonded thio ligands in both complexes. The thio complexes generally undergo a reversible one-electron reduction at potentials significantly more positive than their oxo analogues. The chemical, spectroscopic, and electrochemical properties of the complexes are heavily influenced by the presence of W=S pi frontier orbitals.     

CRYSTAL AND MOLECULAR STRUCTURE OF A NEW ISOMER OF THE COMPLEX W2S4[S2P（OEt）2]2

<正> C8H20O4P2S8W2, Mr = 866. 37, monoclinic, space group P21/ n, α= 10. 122(2),b=12. 813(3),c=18. 267(3) A ;β=90. 25(1)°;7 = 2639(2) A3;Z=4; Dc=2. 43gcm-3;λ(Mo Kα) = 0. 71069A ,μ= 110. 80cm-1,F(000) = 1624,final R = 0. 039 for 2906 observed reflections with I≥3σ(I). The tungsten atom in W2S4[S2P (OEt)2]2 is coordinated by five sulfur atoms,forming a square pyramid. Two WS5 units are linked together by sharing a S-S edge.     

Solid and solution chemistry of protonated and deprotonated mononuclear molybdenum(VI) citrates

Mononuclear molybdenum(VI) citrates with variable degrees of protonation, (NH₄)₂[MoO₂(H₂cit)₂]·H₂O (1), (NH₄)₃[MoO₂(H₂cit)(Hcit)]·H₂O (2) and (NH₄)₅[MoO₂(Hcit)(cit)]·2.5H₂O (3) (H₄cit = citric acid), have been well characterized, where the citrate ligands in 1–3 coordinate bidentate with Mo, while the free carboxylates form very strong hydrogen bonds with α-alkoxy and β-carboxylic acid groups. The chelation of α-alkoxy and α-carboxy groups in citrate are compared with that of FeMo-cofactor in NifV^– Klebsiella pneumoniae nitrogenase. Solution ¹³C NMR spectra show that 1–3 dissociated partly in D₂O. The equilibria are calculated based on ¹H NMR spectra in solution.     

穴状化合物(NH4)16H2[NaSb9 W21O86 ]·15.5H2O的合成及晶体结构

利用Sb2O3,Na2WO4合成了一个巨型的穴状化合物(NH4)16H2[NaSb9W21O86].15.5H2O.晶体衍射数据显示,该化合物属于六方晶系,P6-2c空间群,a=b=1.78025(9)nm,c=2.2510(2)nm,α=β=90(9)°,γ=120(2)°,V=6.1783(7)nm3,Z=2,Dc=3.722Mg/m3,F(000)=6086,μ=21.494mm-1,R1=0.0365,wR2=0.0871[I≥2σ(I)].晶体解析表明,该化合物多阴离子[NaSb9W21O86]18-由3个[SbW7O24]3-亚单元和2个环形的[Sb3O7]5-基团连接形成双环孔穴,一个Na+阳离子通过配位键作用嵌入该空穴内.整个穴状物阴离子呈涡轮状结构,3个[SbW7O24]3-亚单元作为3个叶片.     

Synthesis and Crystal Structure of Ammonium cis-Dioxo Dibenzilato Tungstate （VI） Dihydrate

1 INTRODUCTION Tungsten and molybdenum are chemically analogous elements. Because of their great similari- ties in properties, it was reasonable that the insight into catalytic role of Mo in various enzymes may be provided by replacing Mo with W. In order to un- derstand the chemistry and oxo-transfer properties of these enzymes, numerous dioxo-Mo(VI) and di- oxo-W(VI) complexes with a wide range of ligands have been prepared and structurally characteriz- ed[1～5]. Moreover, hydroxyca…     

A New Heteropolyoxotungstate with a Three-dimensional All-inorganic Framework [（C2H4N2）4（P4Co3W4O（28）H6）（H2C2O4）]n

A new heteropolyoxotungstate [(C2H4N2)4(P4Co3W4O28H6)(H2C2O4)]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1006(17),b = 17.1006(7),c = 10.7525(5),V = 3144.2(2)3,Z = 4,Dc = 3.795 g·cm-3,F(000) = 3300,MoKα(λ = 0.71073 ),μ = 16.460 mm-1,the final R = 0.0335 and wR = 0.0776.In the heteropolyoxotungstate,tungsten-oxygen octahedra are linked by sharing two cis-vertexes into an infinite helical chain extending along the c axis.Cobalt atoms in the octahedral geometry act as the linkers of these chains,forming a three-dimensional framework.The cobalt and phosphorus atoms in the tetrahedral geometry play a role in stabilizing the three-dimensional framework.Ethylenediamine molecules are polymerized into organic chains which locate in the interspaces of the framework in the way of interwinding with the W-O chains.     

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.