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71.
A range of new small bite-angle diphosphine complexes, [M(CO)4{X2PC(R1R2)PX2}] (M = Mo, W; X = Ph, Cy; R1 = H, Me, Et, Pr, allyl, R2 = Me, allyl), have been prepared via elaboration of the methylene backbones in [M(CO)4(X2PCH2PX2)] as a result of successive deprotonation and alkyl halide addition. When X = Ph it proved possible to replace both methylene protons but for X = Cy only one substitution proved possible. This is likely due to the electron-releasing nature of the cyclohexyl groups but may also be due to steric constraints. Attempts to prepare the bis(allyl) substituted complex [Mo(CO)4{Ph2PC(allyl)2PPh2}] were only moderately successful. The crystal structures of nine of these complexes are presented. 相似文献
72.
A novel phosphite-based hetero-polyoxomolybdate, [Mo6(PO3)(HPO3)3O18]9−, has been isolated and structurally characterized. The most striking feature of this polyanion is the presence of peripheral phosphite groups linked to the MoO6 octahedra. In the solid state, this cluster shows strong hydrogen bonding interactions that apparently play a key role in its stabilization and isolation from solution. 相似文献
73.
An air-segmented continuous-flow method has been developed for the determination of molybdenum at ultra trace levels using
the catalytic effect of molybdate during the oxidation of L-ascorbic acid by hydrogen peroxide. Incorporation of an on-line
ion exchange column improved the tolerance limit for various ions. The detection limits with and without the column were 64 pmol L−1 and 17 pmol L−1, and the reproducibilities at 10 nmol L−1 were 2.1% and 0.2%, respectively. The proposed method was applied to the determination of molybdenum in seawater and lake
water as well as in rock and sediment samples. This method has the highest sensitivity among the available literature to our
knowledge, and is also convenient for routine analysis of molybdenum in various natural samples.
Author for correspondence. E-mail: masahito.sugiyama@ sojin0206.mbox.media.kyoto-u.ac.jp
Received October 23, 2002; accepted January 28, 2003
Published online May 19, 2003 相似文献
74.
Susanna Tsang 《Talanta》2007,71(4):1560-1568
A modified molybdenum blue method for fast and accurate measurement of arsenate and phosphate in aqueous solution at concentrations below 10 μmol l−1 is reported. The modification consists of optimizing the composition of the molybdenum-containing solution (potassium antimony tartrate, ammonium molybdate, sulfuric acid).Selective reduction of arsenate by sodium dithionite is used to determine phosphate concentrations, and for the speciation of arsenate and arsenite, in an aqueous mixture according to the scheme developed by Johnston and Pilson. Sodium dithionite is used for the first time to achieve complete, fast (<10 min), and selective reduction of arsenate in neutral solution.These two significant improvements afforded a colorimetric limit for As detection near 1 ppb, which easily meets the requirements imposed by the revised EPA threshold levels for As in drinking water. 相似文献
75.
Reactions of [(dtc)2Mo2(S)2(μ-S)2] with one or two equivalents of CuBr in CH2Cl2 afforded two new heterobimetallic sulfide clusters, [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] (1) and [(dtc)2Mo2(μ3-S)4(CuBr)2] (2). Both compounds were characterized by elemental analysis, IR, UV-vis and X-ray analysis. Compound 1 contains a butterfly-shaped Mo2S4Cu core in which one CuBr unit is coordinated by one bridging S and two terminal S atoms of the [(dtc)2Mo2(S)2(μ-S)2] moiety. In the structure of 2, one [(dtc)2Mo2(S)2(μ-S)2] moiety and two CuBr units are held together by six Cu-μ3-S bonds, forming a cubane-like Mo2S4Cu2 core. 相似文献
76.
The crystal structure of [C10N2H10]2[P2Mo5O21(OH)2] · 2H2O, contains the heteropolyanion, [P2Mo5O21(OH)2]4—, together with diprotonated 4, 4′‐bipyridine. The heteropolyanion is built up from five MoO6 octahedra sharing four common edges and one common corner, capped by two PO3(OH) tetrahedra. The structure is stabilized by hydrogen bonds involving the hydrogen atoms of the 4, 4′‐bipyridine, water molecules and the oxygen atoms of the pentamolybdatobisphosphate. This is the first example that this kind of cluster could be isolated in the presence of a poly‐functional aromatic molecule ion. Crystal data: triclinic, P1¯ (No. 2), a = 9.983(2)Å, b = 11.269(2)Å, c = 17.604(4)Å, α = 73.50(3)°, β = 84.07(3)°, γ = 67.96(3)°; V = 1760.0(6)Å3; Z = 2; R1 = 0.037 and wR2 = 0.081, for 9138 reflections [I > 2σ(I)]. 相似文献
77.
Reactions of MoNCl3 and WNCl3 with Elemental Fluorine. Crystal Structures of [MoO2F2(THF)2] and [WF4(NCl)(CH3CN)] The nitrido chlorides MoNCl3 and WNCl3 as well as WCl4(NCl) react with elemental fluorine forming the N-chloro imido complexes MoF4(NCl) and WF4(NCl), which were characterized by IR spectroscopy. With tetrahydrofurane MoF4(NCl) reacts to give [MoF4(NCl)(THF)], which in THF solution slowly converts into [MoO2F2(THF)2]. From WF4(NCl) with acetonitrile the complex [WF4(NCl)(CH3CN)] is obtained. Both donor acceptor complexes were characterized by crystal structure determinations. [MoO2F2(THF)2] : Space group P21/n, Z = 4, structure solution with 1823 unique reflections, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 636.2, b = 1119.5, c = 1625.2 pm; β = 93.92(1)º. The compound has a monomeric molecular structure with the fluorine atoms in trans-position to one another and with the oxygen atoms of the THF molecules in trans to the oxo ligands. [WF4(NCl)(CH3CN)] : Space group P21/m, Z = 2, structure solution with 1119 unique reflections, R = 0.038 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 511.7, b = 714.9, c = 1002.5 pm; β = 102.59(10)º. The compound has a monomeric molecular structure in which the nitrogen atom of the acetonitrile molecule coordinates in trans-position to the N-chloro imido group W?N? Cl. The structural parameters of this group are WN = 172.2 pm, NCl = 161.1 pm, WNCl = 178.6º. 相似文献
78.
《Journal of Coordination Chemistry》2012,65(4):714-727
Four dioxomolybdenum(VI) complexes were synthesized by reaction of [MoO2(acac)2] with thiosemicarbazones derived from 5-allyl-2-hydroxy-3-methoxybenzaldehyde (1), 2-hydroxynaphthaldehyde (2), 2,3-dihydroxybenzaldehyde (3), or 5-tert-butyl-2-hydroxybenzaldehyde (4). The ligands were coordinated to molybdenum as tridentate ONS donors. X-ray crystallography showed that the distorted octahedral coordination of molybdenum is completed by methanol (D) in 1a, 3a, and 4a or H2O in 2a. The molecular structures of 1, 3, and 4, and the complexes were determined by single-crystal X-ray crystallography. Binding of the ligand and complexes with calf thymus DNA were investigated by UV, fluorescence titrations, and viscosity measurements. Gel electrophoresis revealed that all the complexes can cleave pBR322 plasmid DNA. The cytotoxic properties of the complexes against human colorectal (HCT 116) cell line showed strong antiproliferative activities in relative order 4a?>?3a?>?1a?>?2a with IC50 values of 1.6, 4.0, 4.8, and 6.7?μM, respectively. The complexes exhibited more activity than the standard reference drug, 5-fluorouracil (IC50 7.3?μM). These studies show that dioxomolybdenum(VI) complexes have potential use in chemotherapy. 相似文献
79.
《Journal of Coordination Chemistry》2012,65(5):407-415
The complexes [MI2(CO)3(NCMe)2] (M=Mo or W) react in CH2Cl2 at room temperature with two equivalents of 4,4'-diphenylenecarbonitrile (dpc) to afford the new seven-coordinate complexes, [MI2(CO)3(4,4'-dpc-N)2] (1 and 2) in good yield. Equimolar quantities of [MI2(CO)3(NCMe)2] and PPh3 give [MI2(CO)3(NCMe)(PPh3)], which react in situ with 4,4'-dpc to yield the mono-4,4'-diphenylenecarbonitrile complexes, [MI2(CO)3(4,4'-dpc-N)(PPh3)] (3 and 4). Treatment of the bis(alkyne) complexes, [WI2(CO)(NCMe)(η 2-RC2R)2] (R=Me and Ph) with one equivalent of 4,4'-dpc in CH2Cl2 at room temperature affords the acetonitrile displaced products, [WI2(CO)(4,4'-dpc-N)(η 2-RC2R)2] (5 and 6). Reaction of equimolar quantities of [WI2(CO)(NCMe)(η 2-PhC2Ph)2] and 2 in CH2Cl2 at room temperature gives the 4,4'-dpc-bridged complex, [WI2(CO){WI2(CO)3(4,4'-dpc-N)(4,4'-dpc- N,N')}(η 2-PhC2Ph)2] (7) in good yield. Similarly, equimolar amounts of [WI2(CO)(NCMe)(η 2-RC2R)2] (R=Me and Ph) and (4) react in CH2Cl2 to afford the bimetallic complexes, [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(PPh3)}(η 2-RC2R)2] (8 and 9). The new bimetallic 4,4'-dpc-bridged alkyne complexes, [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(η 2-MeC2Me)2}(η 2-MeC2Me)2] [(10), [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(η 2-PhC2Ph)2}(η 2-PhC2Ph)2] (11) and [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(η 2-MeC2Me)2}(η 2-PhC2Ph)2] (12) are also described. 相似文献
80.
Jiahao Liu Weikang Li Dr. Yinwu Li Prof. Dr. Yan Liu Prof. Dr. Zhuofeng Ke 《化学:亚洲杂志》2021,16(20):3124-3128
The first implementation of a molybdenum complex with an easily accessible bis-N-heterocyclic carbene ligand to catalyze β-alkylation of secondary alcohols via borrowing-hydrogen (BH) strategy using alcohols as alkylating agents is reported. Remarkably high activity, excellent selectivity, and broad substrate scope compatibility with advantages of catalyst usage low to 0.5 mol%, a catalytic amount of NaOH as the base, and H2O as the by-product are demonstrated in this green and step-economical protocol. Mechanistic studies indicate a plausible outer-sphere mechanism in which the alcohol dehydrogenation is the rate-determining step. 相似文献