V^IV(O)(1,4-benzenedicarboxylate) | 410542-58-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: V^IV(O)(1,4-benzenedicarboxylate)
• 英文别名: V^IVO(1,4-benzenedicarboxylate)；V^IV(O)(bdc)；V^IVO(bdc)；vanadium(IV)(O) 1,4-benzenedicarboxylate；VO(1,4-benzenedicarboxylate)；vanadyl(terephthalate)
• CAS: 410542-58-4
• 化学式: C₈H₄O₄*OV
• 分子量: 231.058
• InChiKey: SRGXJWGBTACRFM-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.71
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  97.33
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  V^IV(O)(1,4-benzenedicarboxylate) 、 丙酮 以 neat (no solvent) 为溶剂， 生成 (vanadium(IV)(O) 1,4-benzenedicarboxylate)*(acetone)
  参考文献：
  名称：

  有机分子插入二羧酸钒（IV）的吸附物：被吸附物的结构和有机硫化合物的选择性吸收。

  摘要：

  DOI：

  10.1002/anie.200602556
• 作为产物：
  描述：

  对苯二甲酸 在 HCl 作用下， 以 水 为溶剂， 生成 V^IV(O)(1,4-benzenedicarboxylate)
  参考文献：
  名称：

  有机分子插入二羧酸钒（IV）的吸附物：被吸附物的结构和有机硫化合物的选择性吸收。

  摘要：

  DOI：

  10.1002/anie.200602556

文献信息

• Incorporation of metallocenes into the channel structured Metal–Organic Frameworks MIL-53(Al) and MIL-47(V)
  作者：Mikhail Meilikhov、Kirill Yusenko、Roland A. Fischer

  DOI：10.1039/c0dt00856g

  日期：——

  MIL-53(Al). The inclusion of redox active cobaltocene into MIL-47(V) leads to the formation of a charge transfer compound with a negatively charged framework. The reduction of the vanadium centers is stoichiometric. The resulting material is a mixed valence compound with a V3+/V4+ ratio of 1 : 1. The new compounds were characterized via thermal gravimetric analysis, infrared spectroscopy, solid state NMR

  通过气相的茂金属溶剂费吸附法，获得了具有通道结构MOF（MOF =金属-有机骨架）的茂金属包合物的选择。吸附物结构二茂铁0.5 @ MIL-53（Al）（MIL-53（铝） = [Al（OH）（bdc）] n 与bdc = 1,4-对苯二甲酸酯），二茂铁0.25 @ MIL-47（V）（MIL-47（V）=[V（O）（bdc）] n）， 钴茂0.25 @ MIL-53（铝）， 钴茂0.5 @ MIL-47（V），1-甲酰基二茂铁0.33 @ MIL-53（Al）， 1,1′二甲基二茂铁0.33 @ MIL-53（Al），1,1'-二甲酰基二茂铁0.5 @ MIL-53（Al）由粉末X射线衍射数据确定颗粒，并分析有关客体物质的堆积和取向。与-相比，MIL-47（V）中二茂铁客体分子的堆积显着不同MIL-53（铝） 由于较低的呼吸作用和较弱 氢在MIL-47（V）的情况下，客体分子与宿主网络之
• Reduction of a Metal-Organic Framework by an Organometallic Complex: Magnetic Properties and Structure of the Inclusion Compound [(η5-C5H5)2Co]0.5@MIL-47(V)
  作者：Mikhail Meilikhov、Kirill Yusenko、Antonio Torrisi、Bettina Jee、Caroline Mellot-Draznieks、Andreas Pöppl、Roland A. Fischer

  DOI：10.1002/anie.200907126

  日期：2010.8.16

  The stoichiometric reduction of the MIL‐47(V) framework (see picture; green VO6 octahedra) was performed using cobaltocene as an organometallic reducing agent. The formation of a mixed‐valence compound with a V3+/V4+ ratio of 1:1 was confirmed by magnetic susceptibility measurements. Incorporation of cobaltocene into the MIL‐47(V) framework can be reversed upon treatment with water.

  MIL-47（V）骨架的化学计量还原（参见图片；绿色VO 6八面体）是使用钴茂金属作为有机金属还原剂进行的。V 3+ / V 4+比为1：1的混合价化合物的形成已通过磁化率测量得到证实。用水处理可以逆向将钴茂金属掺入MIL-47（V）骨架中。
• The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene
  作者：Karen Leus、Matthias Vandichel、Ying-Ya Liu、Ilke Muylaert、Jan Musschoot、Steven Pyl、Henk Vrielinck、Freddy Callens、Guy B. Marin、Christophe Detavernier、Paul V. Wiper、Yaroslav Z. Khimyak、Michel Waroquier、Veronique Van Speybroeck、Pascal Van Der Voort

  DOI：10.1016/j.jcat.2011.09.014

  日期：2012.1

  A Metal Organic Framework, containing coordinatively saturated sites linked together by terephthalic linkers (V-MIL-47), is evaluated as a catalyst in the epoxidation of cyclohexene. Different solvents and conditions are tested and compared. If the oxidant TBHP is dissolved in water, a significant leaching of V-species into the solution is observed, and also radical pathways are prominently operative leading to the formation of an adduct between the peroxide and cyclohexene. If, however, the oxidant is dissolved in decane, leaching is negligible and the structural integrity of the V-MIL-47 is maintained during successive runs. The selectivity toward the epoxide is very high in these circumstances. Extensive computational modeling is performed to show that several reaction cycles are possible. EPR and NMR measurements confirm that at least two parallel catalytic cycles are co-existing: one with V+IV sites and one with pre-oxidized V+V sites, and this is in complete agreement with the theoretical predictions. (C) 2011 Elsevier Inc. All rights reserved.
• Separation of Styrene and Ethylbenzene on Metal−Organic Frameworks: Analogous Structures with Different Adsorption Mechanisms
  作者：Michael Maes、Frederik Vermoortele、Luc Alaerts、Sarah Couck、Christine E. A. Kirschhock、Joeri F. M. Denayer、Dirk E. De Vos

  DOI：10.1021/ja106142x

  日期：2010.11.3

  The metal-organic frameworks MIL-47 ((VO)-O-IVO2C-C6H4-CO2}) and MIL-53(Al) (Al-III(OH)center dotO2C-C6H4-CO2}) are capable of separating ethylbenzene and styrene. Both materials adsorb up to 20-24 wt % of both compounds. Despite the fact that they have identical building schemes, the reason for preferential adsorption of styrene compared to ethylbenzene is very different for the two frameworks. For MIL-47, diffraction experiments reveal that styrene is packed inside the pores in a unique, pairwise fashion, resulting in separation factors as high as 4 in favor of styrene. These separation factors are independent of the total amount of adsorbate offered. This is due to co-adsorption of ethylbenzene in the space left available between the packed styrene pairs. The separation is of a non-enthalpic nature. On MIL-53, the origin of the preferential adsorption of styrene is related to differences in enthalpy of adsorption, which are based on different degrees of framework relaxation. The proposed adsorption mechanisms are in line with the influence of temperature on the separation factors derived from pulse chromatography: separation factors are independent of temperature for MIL-47 but vary with temperature for MIL-53. Finally, MIL-53 is also capable of removing typical impurities like o-xylene or toluene from styrene ethylbenzene mixtures.
• Breathing and Twisting: An Investigation of Framework Deformation and Guest Packing in Single Crystals of a Microporous Vanadium Benzenedicarboxylate
  作者：Xiqu Wang、Juergen Eckert、Lumei Liu、Allan J. Jacobson

  DOI：10.1021/ic1025087

  日期：2011.3.7

  The structural details of the compounds vanadium benzenedicarboxylate VO(bdc).Guest, where the Guests are the absorbed six-ring molecules: benzene, 1,4-cyclohexadiene, 1,3-cyclohexadiene, cyclohexene and cyclohexane, have been determined from single crystal X-ray data. All of the six-ring guest molecules show a high degree of ordering inside the channels of VO(bdc). The interactions between the guests and the host framework are dominated by van der Waals bonding. The six-ring molecules are all packed in two columns in the channels, either in herringbone or close to parallel patterns. The packing changes the space group symmetry of VO(bdc) from Pnma to the noncentrosymmetric space group P2(1)2(1)2(1). The VO(bdc) framework deforms to closely adapt to the shape and thickness changes of the double columns of the guest molecules. In addition to the well studied breathing deformation, a twisting deformation mechanism that involves a cooperative rotation of the octahedral chains accompanied by bending of the bdc ligand is apparent in the detailed structural data. More quantitative information on the remarkable flexibility of the VO(bdc) framework was obtained from ab initio calculations.