methanol,oxotungsten | 19174-06-2

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: methanol,oxotungsten
• 英文别名: tungsten oxomethoxide；W(O)(OMe)₄；WO(OMe)₄；WO(OMe)4；Wolfram-(VI)-saeure-tetramethylester
• CAS: 19174-06-2
• 化学式: C₄H₁₂O₅W
• 分子量: 323.986
• InChiKey: NATFYGVXIVQQKF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.27
• 重原子数：
  10.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  methanol,oxotungsten 以 水 为溶剂， 生成 tungsten(VI) oxide
  参考文献：
  名称：

  Synthesis of WO₃ Nanorods by Reacting WO(OMe)₄ under Autogenic Pressure at Elevated Temperature Followed by Annealing

  摘要：

  This article reports on the fabrication of WO3 nanorods using an efficient straightforward synthetic technique, without a catalyst, and using a single precursor. The thermal dissociation of WO(OMe)(4) at 700 degrees C in a closed Swagelok cell under an air/inert atmosphere yielded W18O49 nanorods. Annealing Of W18O49 at 500 degrees C under an air atmosphere led to the formation of pure WO3 nanorods. The obtained products are characterized by morphological (scanning electron microscopy and transmission electron microscopy), structural (X-ray diffraction analysis, high-resolution scanning electron microscopy, and Raman spectroscopy), and compositional [energy-dispersive X-ray and elemental (C, H, N, S) analysis] measurements. The mechanism of the formation of nonstoichiometric W18O49 nanorods is supported by the measured analytical data and several control experiments.

  DOI：

  10.1021/ic051179n
• 作为产物：
  描述：

  氧代氯化钨 在 methanol 、 Na 作用下， 以 甲醇 、 乙醚 为溶剂， 以>99的产率得到methanol,oxotungsten
  参考文献：
  名称：

  Kucheiko, S. I.; Turova, N. Ya.; Kozlova, N. I., Koordinatsionnaya Khimiya, 1985, vol. 11, p. 867 - 875

  摘要：

  DOI：
• 作为试剂：
  描述：

  芳樟醇 在 吡啶 、 methanol,oxotungsten 作用下， 反应 3.0h， 生成 橙花醇 、 香叶醇
  参考文献：
  名称：

  SELECTIVE ALLYLIC REARRANGEMENT WITH TUNGSTEN CATALYST

  摘要：

  烯丙醇的选择性热重排在各种 O=W(OR)4 存在下进行。比O=W(OR)4催化剂更稳定，比O=V(OR)3催化剂活性高数倍的配体催化剂。

  DOI：

  10.1246/cl.1982.357

文献信息

• Activation of H₂O₂ over Zr(IV). Insights from Model Studies on Zr-Monosubstituted Lindqvist Tungstates
  作者：Nataliya V. Maksimchuk、Vasilii Yu. Evtushok、Olga V. Zalomaeva、Gennadii M. Maksimov、Irina D. Ivanchikova、Yuriy A. Chesalov、Ilia V. Eltsov、Pavel A. Abramov、Tatyana S. Glazneva、Vadim V. Yanshole、Oxana A. Kholdeeva、R. John Errington、Albert Solé-Daura、Josep M. Poblet、Jorge J. Carbó

  DOI：10.1021/acscatal.1c02485

  日期：2021.8.20

  (Bu4N)2[W5O18Zr(H2O)3] (1) and (Bu4N)6[W5O18Zr(μ-OH)}2] (2), have been employed as molecular models to unravel the mechanism of hydrogen peroxide activation over Zr(IV) sites. Compounds 1 and 2 are hydrolytically stable and catalyze the epoxidation of C═C bonds in unfunctionalized alkenes and α,β-unsaturated ketones, as well as sulfoxidation of thioethers. Monomer 1 is more active than dimer 2. Acid

  Zr-单取代的 Lindqvist 型多金属氧酸盐 (Zr-POM)，(Bu 4 N) 2 [W 5 O 18 Zr(H 2 O) 3 ] ( 1 ) 和 (Bu 4 N) 6 [W 5 O 18 Zr( μ-OH)} 2 ] ( 2 )，已被用作分子模型来揭示过氧化氢在 Zr(IV) 位点上的活化机制。化合物1和2具有水解稳定性，可催化未官能化烯烃和 α,β-不饱和酮中 C=C 键的环氧化以及硫醚的磺化氧化。单体1比二聚体2更活跃。酸添加剂大大加速了氧化反应，并将氧化剂利用效率提高到>99%。产物分布表明异裂氧转移机制，该机制涉及在 Zr-POM 和 H 2 O 2相互作用时形成的亲电氧化物质。1和2与 H 2 O 2的相互作用以及由此产生的过氧衍生物已通过 UV-vis、FTIR、拉曼光谱、HR-ESI-MS 和组合 HPLC-ICP-原子发射光谱技术进行了研究。一个之间的相互作用17
• [EN] METAL ORGANIC COMPOUNDS<br/>[FR] COMPOSÉS ORGANOMÉTALLIQUES
  申请人：UMICORE AG & CO KG

  公开号：WO2021197597A1

  公开（公告）日：2021-10-07

  The invention concerns a process for preparing an essentially silicon (Si) free compounds of the general formula [M(O)(OR)y], wherein M = Mo, y = 3 or M = W, y = 3 or 4. Furthermore, it is directed towards compounds obtained by the aforementioned process and towards the use of such an obtained compound. Another objective of the herein described invention are essentially silicon free compounds of the general formula MOXy or [MOXy(solv)p], prepared using the aforementioned process, wherein M = Mo, y = 3 or M = W, y = 3 or 4, X = Cl or Br, solv = an oxidizing agent Z binding or coordinating to M via at least one donor atom, p = 1 or 2. The invention is also directed towards the use of essentially silicon free compounds prepared using the aforementioned process of the general formula MOXy or [MOXy(solv)p].

  该发明涉及一种制备通式[M(O)(OR)y]的基本无硅（Si）化合物的过程，其中M = MO，y = 3或M = W，y = 3或4。此外，它针对通过上述过程获得的化合物以及利用这种获得的化合物的用途。所述发明的另一个目标是使用上述过程制备的通式MOXy或[MOXy(solv)p]的基本无硅化合物，其中M = MO，y = 3或M = W，y = 3或4，X = Cl或Br，solv = 通过至少一个供体原子与M结合或配位的氧化剂Z，p = 1或2。该发明还涉及利用利用上述通式MOXy或[MOXy(solv)p]的基本无硅化合物的方法。
• Synthesis and Reactivity of the Methoxozirconium Pentatungstate (<i>ⁿ</i>Bu₄N)₆[{(μ-MeO)ZrW₅O₁₈}₂]:  Insights into Proton-Transfer Reactions, Solution Dynamics, and Assembly of {ZrW₅O₁₈}²^- Building Blocks
  作者：R. John Errington、Sagar S. Petkar、Paul S. Middleton、William McFarlane、William Clegg、Robert A. Coxall、Ross W. Harrington

  DOI：10.1021/ja0725495

  日期：2007.10.1

  and n = 1 for 4-8, while 1H and 17O NMR studies of hydrolysis of 1 revealed the formation of an intermediate [(mu-MeO)(mu-HO)(ZrW5O18)2]6-. Electrospray ionization mass spectrometry of 1 and 3 illustrated the robust nature of the ZrW5O18 framework, and X-ray crystal structure determinations showed that steric interactions between ligands X and the ZrW5O18 surface are important. The coordination number

  通过 Zr(OnPr)4 的化学计量水解合成了甲氧基桥接的二聚体 ZrIV 取代的 Lindqvist 型多金属氧酸盐 (POM) (nBu4N)6[(mu-MeO)ZrW5O18}2], (TBA)61 , [Zr(OiPr)3(mu-OnPr)(iPrOH)}2], 或 [Zr(OiPr)4(iPrOH)}2] 和 [WO(OMe)4}2] 在 ( nBu4N)2WO4，首次提供了 ZrW5 POM 的系统非水化学方法，并为 17O NMR 研究提供了获取富含 17O 样品的有效途径。1H NMR 没有提供 1 在溶液中解离的证据，尽管 EXSY 研究表明与 MeOH 的交换很慢。在升高的温度下与 HX 反应产生一系列阴离子 [XZrW5O18}n]3n- (X = OH, 3; OPh, 4; OC6H4Me-4, 5; OC6H4(CHO)-2, 6; acac, 7; OAc
• Alkoxide hydrolysis as a route to early transition-metal polyoxometalates: synthesis and crystal structures of heteronuclear hexametalate derivatives
  作者：William Clegg、Mark R. J. Elsegood、R. John Errington、Joanne Havelock

  DOI：10.1039/dt9960000681

  日期：——

  Oxygen-17 NMR studies indicated that the hexametalates [MW5O19]n– or their derivatives [(MeO)MW5O18](n–1)–(M = Ti, Zr, V, Nb, Ta, Mo or W) can be obtained by hydrolysis of the appropriate mixture of metal alkoxides in the presence of M′O42–(M′= W or Mo) with remarkable selectivity in some cases, giving a very efficient method of preparing 17O-enriched polyoxometalates. The crystal structure of [NBun4]3[(MeO)TiW5O18]·0.5MeCN shows the terminal Ti–OMe bond in the anion to have Ti–O 1.760(10)Å and Ti–O–C 150.1(12)° and also reveals W–O bridging bond length alternations due to the substitution of Ti(OMe)3+ for WO4+ in the [W6O19]2– structure. Hydrolysis of [NBun4]2[(MeO)NbW5O18] gives [NBun4]4[(NbW5O18)2O] and the crystal structure revealed two eclipsed NbW5O18 oxide fragments joined by a strictly linear Nb–O–Nb linkage with Nb–O 2.264(8)Å.

  氧-17 NMR 研究表明，在 M′O42-（M′= W 或 Mo）存在下，通过水解适当的金属烷氧基化物混合物，可以获得六金属盐 [MW5O19]n- 或其衍生物 [(MeO)MW5O18](n-1)-（M = Ti、Zr、V、Nb、Ta、Mo 或 W），在某些情况下具有显著的选择性，这为制备富含 17O 的多氧金属盐提供了一种非常有效的方法。[NBun4]3[(MeO)TiW5O18]-0.5MeCN的晶体结构显示，阴离子中的末端Ti-OMe键的Ti-O为1.760(10)埃，Ti-O-C为150.1(12)°，还显示了由于[W6O19]2-结构中Ti(OMe)3+取代WO4+而引起的W-O桥键长度交替。水解[NBun4]2[(MeO)NbW5O18]可得到[NBun4]4[(NbW5O18)2O]，其晶体结构显示了由严格线性 Nb-O-Nb 连接（Nb-O 2.264(8)埃）连接的两个黯淡的 NbW5O18 氧化物片段。
• Solution interaction of O-donor ligand metal complexes with thiocarbonyl compounds—a new general route to metal sulfide materials
  作者：Gulaim A. Seisenbaeva、Suresh Gohil、Kjell Jansson、Konrad Herbst、Michael Brorson、Vadim G. Kessler

  DOI：10.1039/b300398c

  日期：——

  reaction within a mesoporous alumina matrix, supported metal sulfide catalysts were obtained in one step. These catalysts were tested for catalytic hydrodesulfurization and their activity compared with catalysts prepared by traditional methods. Reaction of nickel and zinc acetylacetonates and aminoalkoxides with DMTF in hydrocarbon media was found to provide colloids and, on aging, fine powder precipitates

  钼和钨氧代烷氧化物[MO（OMe）4 ]; M = MO，W}和七氧化二（（Re 2 O 7）在室温下与硫代羰基化合物 如 N，N-二甲硫基甲酰胺 （DMTF），产生结晶金属 硫化物MOS 2，WS 3和Re 2 S 7。作为第一步，反应机理涉及通过硫供体原子使DMTF与金属配位，然后使后者与双键氧原子复分解。根据反应条件，最终产物是胶体金属硫化物 或最大0.1毫米的金属 硫化物晶体。通过在介孔氧化铝中进行反应矩阵，支持金属 硫化物 催化剂只需一步即可获得。这些催化剂 进行了催化加氢脱硫的试验，并比较了其活性。 催化剂用传统方法准备的。乙酰丙酮镍和锌和氨基醇盐与DMTF的反应烃 发现介质可提供胶体，并且在老化时会产生细小的NiS和ZnS粉末沉淀。