Synthesis and structure of hexabenzyl-dimolybdenum (MoMo)

The homoleptic benzyl Mo₂(CH₂Ph)₆ has been obtained by reaction of either MoCl₄(thf)₂ or Mo₂(OPrⁱ)₆ with Mg(CH₂Ph)₂. The dark-red, sparingly soluble complex has been characterized by ¹H and ¹³C NMR as well as by a solid-state structure analysis. Pertinent bond distances (Å) and angles (°) for the unbridged, ethane-like molecule which contains crystallographic S₆-symmetry are: MoMo = 2.175(1), MoC = 2.162(2), MoMoC = 97.61(6), and MoCC(Ph) = 98.9(1).     

Analysis of the metal–ligand bonds in [Mo(X)(NH2)3] (X = P, N, PO, and NO), [Mo(CO)5(NO)]+, and [Mo(CO)5(PO)]+

Quantum chemical calculations at the DFT level have been carried out for model complexes [Mo(P)(NH₂)₃] (1), [Mo(N)(NH₂)₃] (2), [Mo(PO)(NH₂)₃] (3), [Mo(NO)(NH₂)₃] (4), [Mo(CO)₅(PO)]⁺ (5), and [Mo(CO)₅(NO)]⁺ (6). The equilibrium geometries and the vibration frequencies are in good agreement with experimental and previous theoretical results. The nature of the Mo–PO, Mo–NO, Mo–PO⁺, Mo–NO⁺, Mo–P, and Mo–N bond has been investigated by means of the AIM, NBO and EDA methods. The NBO and EDA data complement each other in the interpretation of the interatomic interactions while the numerical AIM results must be interpreted with caution. The terminal Mo–P and Mo–N bonds in 1 and 2 are clearly electron-sharing triple bonds. The terminal Mo–PO and Mo–NO bonds in 3 and 4 have also three bonding contributions from a σ and a degenerate π orbital where the σ components are more polarized toward the ligand end and the π orbitals are more polarized toward the metal end than in 1 and 2. The EDA calculations show that the π bonding contributions to the Mo–PO and Mo–NO bonds in 3 and 4 are much more important than the σ contributions while σ and π bonding have nearly equal strength in the terminal Mo–P and Mo–N bonds in 1 and 2. The total (NH₂)₃Mo–PO binding interactions are stronger than for (NH₂)₃Mo–P which is in agreement with the shorter Mo–PO bond. The calculated bond orders suggest that there are only (NH₂)₃Mo–PO and (NH₂)₃Mo–NO double bonds which comes from the larger polarization of the σ and π contributions but a closer inspection of the bonding shows that these bonds should also be considered as electron-sharing triple bonds. The bonding situation in the positively charged complexes [(CO)₅Mo–(PO)]⁺ and [(CO)₅Mo–(NO)]⁺ is best described in terms of (CO)₅Mo → XO⁺ donation and (CO)₅Mo ← XO⁺ backdonation (X = P, N) using the Dewar–Chatt–Duncanson model. The latter bonds are stronger and have a larger π character than the Mo-CO bonds.     

Mo(W)-Co(Ni,Fe)簇合物的加氢脱硫催化活性

对线型、立方烷型和笼状３种不同构型的Ｍｏ（Ｗ）－Ｃｏ（Ｎｉ，Ｆｅ）－Ｓ（Ｏ）簇共１２种化俣物进行了噻吩加氢硫和环己烯加氢的催化活性研究，讨论了簇合物的组成，金属原子的配比、价态与催化活性的关系，探讨了不同构型对活性的影响。     

Kristallchemische Untersuchungen in Systemen (Ti,Nb, Ta,Mo, W)−(As,Sb)

Zusammenfassung Legierungen aus den Systemen Mo–As und W–As werden röntgenographisch untersucht. Die Kristallstrukturen von MoAs und Mo₅As₄ werden bestimmt. MoAs kristallisiert im B31-Typ, Mo₅As₄ und die dazu isotypen Verbindungen (Ti_0,4W_0,6)₅As₄; Nb₅Sb₄ und Ta₅Sb₄ gehören zu einer Ti₅Te₄-artigen Struktur.     

(K,Mo)Y分子筛中钼组分的EXAFS研究

应用同步辐射Extended X-ray Absorption Fine Structure (EXAFS)技术研究固态法制备的KHMoY分子筛的氧化态和硫化态样品以及硫化态KHY/MoO3样品中钼组分的局域配位环境结构,并与KHMoY和KHY/MoO3样品催化加氢活性结果进行对照.结果表明,随原子比(K+2Mo)/Al的变化,钼原子周围的配位环境有显著的差异.当(K+2Mo)/Al＜1时,KHMoY和KHY/MoO3硫化后,钼组分主要以MoS2小原子簇分散在分子筛超笼中;(K+2Mo)/Al＞1时,钼组分则有两种存在环境,即分子筛超笼中的和分子筛外表面的钼组分.分子筛超笼中的MoS2原子簇的催化加氢合成醇选择性较高;分子筛外表面的MoS2微小颗粒的尺寸相对于超笼中的要大许多,其合成醇选择性较低.     

Nd_(1-y)Dy_yFe_(11-x)TiM_x(M=Mo,Si)系列化合物中Mo,Si元素的掺杂对其结构及磁性能的影响

通过电弧方法制备了一系列的Nd1-yDyyFe11-xTiMx(M=Mo,Si)型稀土过渡金属化合物,并且通过X射线衍射和中子衍射对其晶体结构进行了研究.实验发现,Nd1-yDyyFe11-xTiMx(M=Mo,Si)系列中化合物主要结构为ThMn12-type(1︰12相).Dy取代Nd没有明显影响1︰12相形成的含量.在Nd0.5Dy0.5Fe11-xTiMx(M=Mo,Si)系列中,当x≤0.8时Nd0.5Dy0.5Fe11-xTiMox化合物主要呈ThMn12-type晶形,当x0.8时,化合物中1︰12相的含量降至80%以下;对于Nd0.5Dy0.5Fe11-xTiSix,当x≤0.6时,Nd0.5Dy0.5Fe11-xTiSix化合物主要呈ThMn12-type晶形,当x0.6时,化合物中1︰12相的含量降至90%以下但保持在80%以上.在不同的化合物中,稳定元素的含量不同.ThMn12-type相的百分含量随着Mo和Si取代Fe含量的增加而减小,意味着Mo和Si取代更多的Fe时,ThMn12-type相将变得不稳定.Nd0.5Dy0.5Fe11-xTiMox化合物的晶格参数a和c以及晶胞体积V随着Mo(x)含量的增加呈线性增加是因为Mo的原子半径比其中的Fe的大;而Nd0.5Dy0.5Fe11-xTiSix合金的晶格参数a和c以及晶胞体积V随着Si(x)含量的增加呈线性减小是因为Si的原子半径比其中的Fe的小.在NdyDy1-yFe11-xTiMx(M=Mo,Si)中,因为Ti和Mo的半径比Fe大而Si的半径比Fe小,所以Ti和Mo原子优先占据8i晶位,Si原子优先占据8j和8f晶位.在化合物RFe12-xMx中,居里温度由T-T交换作用决定的,由于T-T交换作用依赖于T-T原子距离,因此其他元素对Fe的取代导致了居里温度的改变.磁性测量表明Mo或Si取代Fe均导致居里温度的降低.     

Reduktive CC-kupplung von zwei isocyanid-liganden an Mo(II)- und W(II)-zentren,eine reaktionssequenz über isocyanid- und aminocarbin-komplexe von Mo(0) und W(0)

The octahedral alkylisocyanide complexes M(RNC)₆ and alkylisocyanide-substituted aminocarbyne complexes [(RNC)₅MCN(Et)R]BF₄ (M = Mo, W; R = Et, ^tBu) have been found to be key intermediates in the reductive coupling of two isocyanide ligands to a complexed alkyne. The crucial step in the reaction sequence leading from the seven-coordinate starting materials [M(RNC)₆Br]Br to the bis(amino)acetylene products [I(RNC)₄M[η²-R(Et)NCCN(H)R]]BF₄ and [I(RNC)₄M[η²-R(H)NCCN(H)R]]I involves an aminocarbyne-isocyanide coupling reaction induced by HI. The composition and structure of the intermediates and the products have been fully characterized.     

Photochemical reactions of M(CO)5THF (M = Cr, Mo, W) with thio Schiff bases

The hitherto unknown complexes, [M₂(CO)₆(μ-CO)(μ-L)], [M = Cr; 1, Mo; 2, W; 3] and [M₂(CO)₆(μ-CO)(μ-L′)], [M = Cr; 4, Mo; 5, W; 6] have been synthesized by the photochemical reactions of photogenerated intermediate, M(CO)₅THF (M = Cr, Mo, W) with thio Schiff base ligands, N,N′-bis(2-aminothiophenol)-1,4-bis(2-carboxaldehydephenoxy)butane (H ₂ L) and N,N′-bis(2-aminothiophenol)-1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane (H ₂ L′). The complexes have been characterized by elemental analysis, LC-mass spectrometry, magnetic studies, FT-IR and ¹H NMR spectroscopy. The spectroscopic studies show that H ₂ L and H ₂ L′ ligands are converted to benzothiazole derivatives, L and L′ after UV irradiation and coordinated to the central metal as bridging ligands via the central azomethine nitrogen and sulphur atoms in 1–6.     

An alternative route for the preparation of the medical isotope 99Mo from the 238U(γ, f) and 100Mo(γ, n) reactions

The radionuclide ⁹⁹Mo, which has a half-life of 65.94 h was produced from ²³⁸U(γ, f) and ¹⁰⁰Mo(γ, n) reactions using a 10 MeV electron linac at EBC, Kharghar Navi-Mumbai, India. This has been investigated since the daughter product ^99mTc is very important from a medical point of view and can be produced in a generator from the parent ⁹⁹Mo. The activity of ⁹⁹Mo was analyzed by a γ-ray spectrometric technique using a HPGe detector. From the detected γ-rays activity of 140.5 and 739.8 keV, the amount of ⁹⁹Mo produced was determined. For comparison, the amount of ⁹⁹Mo from ²³⁸U(γ, f) and ¹⁰⁰Mo(γ, n) reactions was also estimated using the experimental photon flux from ¹⁹⁷Au(γ, n)¹⁹⁶Au reaction. The amount of ⁹⁹Mo from the detected γ-lines is in agreement with the estimated value for ²³⁸U(γ, f) and ¹⁰⁰Mo(γ, n) reactions. The production of ⁹⁹Mo activity from ²³⁸U(γ, f) and ¹⁰⁰Mo(γ, n) reactions is a relevant and novel approach, which provides alternative routes to ^235,238U(n, f) and ⁹⁸Mo(n, γ) reactions, circumventing the need for a reactor. The viability and practicality of the ⁹⁹Mo production from the ²³⁸U(γ, f) and ¹⁰⁰Mo(γ, n) reactions alternative to ^235,238U(n, f) and ⁹⁸Mo(n, γ) reactions has been emphasize. An estimate has been also arrived based on the experimental data of present work to fulfill the requirement of DOE.     

Chemical effects of (n, γ) nuclear reaction on (Mo6Cl8)Cl4

The chemical effects of⁹⁸Mo(n, )⁹⁹ Mo reaction on molybdenum(II) chloride [(Mo₆Cl₈)Cl₄] have been studied. Retention, thermal and radiolytical annealing were determined. It was found that this molybdenum compound has low retention, a negligible tendency to thermal annealing and a virtual insensitivity to hydrolysis. For practical application in the enrichment of⁹⁹Mo by the Shilard-Chalmers method, molybdenum(II) chloride [(Mo₆Cl₈)Cl₄] appears to offer good prospects.     

Nd(Fe,Mo)_(12)N_x磁粉的内禀磁性与永磁性能

本文在研究Nd(Fe,Mo)_(12)N_x的形成条件、结构特点和内禀磁性的基础上,制备了Nd(Fe,Mo)_(12)N_x型永磁体。采用常规球磨的方法,制成各向异性磁粉,矫顽力_iH_c可达501.7 kA/m(6.3 kOe)。研究了矫顽力与微粉颗粒度的关系。发现具有高矫顽力的微粉,对应为小于1μm的单晶颗粒。利用机械合金化工艺制成的磁粉,矫顽力_iH_c可达692.3 kA/m(8.7 kOe),并具有明显的钉扎特征。各向异性磁粉的最大磁能积为95.5 kJ/m~3(12.0 MGOe)。研究了上述两类磁粉矫顽力和剩余磁感应强度随温度的变化,并与Nd_2Fe_(14)B型磁体矫顽力的温度性能进行了对比。     

紫外激光诱导C60与M(CO)6(M=Cr,Mo, W)的配位反应

研究了用紫外激光(355 nm)诱导C_(60)与金属羰基化合物M(CO)_6(M＝Cr；Mo，W)的配位反应，合成了具有C_(4υ)对称性的配位络合物(η~2－C_(60))M(CO)_5，并初步讨论了C_(60)与M(CO)_6反应的动力学过程．     

金属羰基化合物M(CO)6(M=Cr,Mo, W)氧原子转移反应动力学与机理

本文研究了PPh3存在与不存在的情况下, M(CO)6(M=Cr, Mo, W)与三甲胺氧化物me3NO在CH2Cl2中的氧原子转移反应动力学. 反应速率遵循: r=k[M(CO)6][Me3NO], 并且rW>rMo>rCr, 并根据实验结果提出了反应机理, 讨论了溶剂对反应速率的影响.     

Correlation between solvatochromism and back-bonding in four isomeric (α-diimine)M(CO)4 complexes,M = Cr,Mo, W

Long-wavelength charge transfer absorption energies of isomeric complexes (bidiazine)M(CO)₄, (bidiazine = 3,3′-bipyridazine, 2,2′- and 4,4′-bipyrimidine, 2,2′-bipyrazine; M = Cr, Mo, W) were measured in various solvents and compared with those for corresponding 2,2′-bipyridine complexes. Linear correlations of energies of absorption maxima with solvent parameters E_MLCT revealed that the solvent dependence Δυ/gDE_MLCT within the bidiazine series increases with decreasing absolute charge transfer transition energy in a given solvent, i.e. with increasing back-donation into the ligand π orbital. Complexes of the most strongly back-bonding ligand, 4,4′-bipyrimidine, thus display by far the most pronounced solvent dependence, with Δυ/gdE_MLCT 4100 cm ⁻¹ for the molybdenum system.     

补充钼(Mo)元素的食疗方法

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补充钼(Mo)元素的食疗方法

正若缺钼,则伤骨,常见到,牙齿落,再发展,骨质变,既松软,骨质变,既松软,又无力,若不治,还会得,白血病,食道癌,此病得,初难找,无病因,无脉象,成年人,不明显,幼儿们,最突出,早落齿,迟行走,食疗法,最应手。其一法:麦饭石,五百克,经炮制,研为末,入水缸,过滤水,经饮用,数日愈。其二法:取卤碱,五克整,放水内,加板栗,     

Diamagnetic anisotropy of the MoMo bond in Mo2(O2CR)4 type complexes

By using newer structural and NMR data for Mo₂(O₂CR)₄ compounds with R = PhCH(OH) and CH₃ the diamagnetic anisotropy of the Mo-Mo quadruple bonds has been estimated as −(210±30) × 10⁻³⁶ m³ per molecule.     

Mo(W)-Cu(Ag)-S原子簇化合物的研究现状

本文在研究Ｍｏ（Ｗ）－Ｃｕ（Ａｇ）－Ｓ原子簇化合物的低热固态合成化学基础上，详细地对该类簇合物进行了归纳，从中提出；１，ＭＯ４－ｎＳｎ＾２＾－（Ｍ＝Ｍｏ，Ｗ；ｎ＝２，３，４）作为配体中心。２，氧原子在簇合物中仅作为端基，不参与同其他金属成键。３，单个ＭＳ４（Ｍ＝Ｍｏ，Ｗ）基团最多只能键合六个Ｃｕ（Ａｇ）原子，即最大核数为七。４，迄今为止所有Ｍｏ（Ｗ）－Ｃｕ－Ｓ原子簇化合物中Ｃｕ均为＋１价。５，预计