tetrabutylammonium chromate

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: tetrabutylammonium chromate
• 英文别名: (Bu4N)2[CrO4]
• 化学式: 2C₁₆H₃₆N*CrO₄
• 分子量: 600.931
• InChiKey: WUMRFQGFKRNDCT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.39
• 重原子数：
  22.0
• 可旋转键数：
  12.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  80.26
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  tetrabutylammonium chromate 、 重氧水 以 乙腈 为溶剂， 生成 (Bu4N)2[Cr(18)O4]
  参考文献：
  名称：

  Gas-Phase Reactivity of Heterobinuclear Oxometalate Anions [CrMoO₆(OR)]^-, [CrWO₆(OR)]^-, and [MoWO₆(OR)]^- (R = H, ⁿBu)

  摘要：

  Heterobinuclear oxometalate anions based upon [CrMoO7](2-), [CrWO7](2-), and [MoWO7](2-) were generated and transferred to the gas phase by the electrospray process from acetonitrile solutions containing two of the salts (Bu4N)(2)[MO4] (M = Cr, Mo, W). Their reactivities were examined and compared with those of the related homobinuclear anions based upon [M2O7](2-) (M = Cr, Mo, W). Particular emphasis was placed upon reactions relevant to gas-phase catalytic cycles described previously for oxidation of alcohols by [Mo2O6(OH)](-) (Waters, T.; O'Hair, R. A. J.; Wedd, A. G. J. Am. Chem. Soc. 2003, 125, 3384-3396). The protonated anions [MM'O-6(OH)](-) each reacted with methanol with loss of water to form [MM'O-6(OCH3)](-) at a rate that was intermediate between those of [M2O6(OH)](-) and [M'O-2(6)(OH)](-). The butylated anions [MM'O-6(OBu)](-) were generated by collisional activation of the ion-pairs {Bu4N+[MM'O-7](2-)}(-). Collisional activation of [MM'O-6(OBu)](-) resulted in either the loss of butanal (redox reaction) or the loss of butene (elimination reaction), with the detailed nature of the observations depending on the nature of both M and M'. Selective O-18 labeling indicated that the butoxo ligands of [CrMoO6(OBu)](-) and [CrWO6(OBu)](-) were located on molybdenum and tungsten, respectively. This structural insight allowed a more detailed comparison of reactivity with the homobinuclear species, and highlighted the importance of the neighboring metal center in these reactions.

  DOI：

  10.1021/ic050288z
• 作为产物：
  描述：

  chromium(VI) oxide 、 tetra-n-butylammonium hydroxide 以 not given 为溶剂， 生成 tetrabutylammonium chromate
  参考文献：
  名称：

  由 EO4– (E = Cl, Re) 和 EO42– 氧阴离子 (E = S, Cr, Mo, W) 连接的双核 NiIII 胺-硫酚盐配合物的制备和表征

  摘要：

  双电荷 EO 4 2- 基团与 [(L Me )-Ni 2 ) 2+ 碎片的相互作用比 EO 4 - 基团更强烈，如 Ni-O 距离所反映的，Ni-O 距离在 2 和 3 中比在 4 中显着更长-7. 4 和 6 中的镍 (II) 离子弱铁磁耦合（分别为 J = 24.8 和 3.75 cm-1），耦合的大小似乎与 Ni-S-Ni 角相关。

  DOI：

  10.1002/ejic.200700015
• 作为试剂：
  描述：

  苯酚 在 tetrabutylammonium chromate 、 sodium nitrite 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以36%的产率得到对硝基苯酚
  参考文献：
  名称：

  非质子条件下铬酸四丁铵和重铬酸钾的酚类化合物硝化和对苯二酚的氧化

  摘要：

  在这项工作中，我们已经报道了一种温和，有效和选择性的方法，该方法用于在重铬酸四丁铵（TBAD）存在下，使用亚硝酸钠将酚类化合物单硝化，以及在CH 2 Cl 2中用TBAD将对苯二酚氧化为醌。使用该方法，在中性非质子条件下可获得高产率的硝基酚和醌。铬酸四丁铵（TBAC）在相同条件下也可用作氧化剂。 在重铬酸四丁铵（TBAD）和铬酸四丁铵（TBAC）存在下，使用亚硝酸钠在中性非质子条件下温和有效地进行酚类化合物的单硝化。另外，对苯二酚很容易被TBAD和TBAC氧化为醌。

  DOI：

  10.1007/s12039-011-0062-y

文献信息

• Hydrates of Organic Compounds. VII. The Effect of Anions on the Formation of Clathrate Hydrates of Tetrabutylammonium Salts
  作者：Haruo Nakayama

  DOI：10.1246/bcsj.56.877

  日期：1983.3

  Phase diagrams of the binary mixtures of tetrabutylammonium salt [(n-C4H9)4N]nX (X=NO2, NO3, BrO3, ClO3, IO3, ClO4, MnO4, and NCS for n=1; X=CO3, SO4, WO4, and CrO4 for n=2; and X=PO4 for n=3) with water were determined over the temperature range between −10 and +50 °C. From these diagrams the following results were obtained: (1) the formation of a clathrate-like hydrate for salts having such anions

  四丁基铵盐 [(n-C4H9)4N]nX（X=NO2、NO3、BrO3、ClO3、IO3、ClO4、MnO4 和 NCS，n=1；X=CO3、SO4、WO4、和 CrO4（n=2）；X=PO4（n=3）与水在 -10 至 +50 °C 的温度范围内测定。从这些图表中获得了以下结果： (1) 新确认了具有诸如 NO2-、NO3-、BrO3-、ClO3-、IO3-、SO42- 和 PO43- 等阴离子的盐类形成包合物状水合物; (2)一价阴离子盐的笼形水合物的熔点受阴离子种类的明显影响；(3)在具有二价或三价阴离子的盐的水合物中，熔点相对较高并且受阴离子种类的影响很小；(4) 从水合数来看，这些水合物的晶体结构与四丁基氟化铵水合物的晶体结构基本相同；(5)高锰酸盐和高氯酸盐在水中的溶解度均显着低于...
• Gas-Phase Reactivity of Heterobinuclear Oxometalate Anions [CrMoO₆(OR)]^-, [CrWO₆(OR)]^-, and [MoWO₆(OR)]^- (R = H, <i>ⁿ</i>Bu)
  作者：Tom Waters、Richard A. J. O'Hair、Anthony G. Wedd

  DOI：10.1021/ic050288z

  日期：2005.5.1

  Heterobinuclear oxometalate anions based upon [CrMoO7](2-), [CrWO7](2-), and [MoWO7](2-) were generated and transferred to the gas phase by the electrospray process from acetonitrile solutions containing two of the salts (Bu4N)(2)[MO4] (M = Cr, Mo, W). Their reactivities were examined and compared with those of the related homobinuclear anions based upon [M2O7](2-) (M = Cr, Mo, W). Particular emphasis was placed upon reactions relevant to gas-phase catalytic cycles described previously for oxidation of alcohols by [Mo2O6(OH)](-) (Waters, T.; O'Hair, R. A. J.; Wedd, A. G. J. Am. Chem. Soc. 2003, 125, 3384-3396). The protonated anions [MM'O-6(OH)](-) each reacted with methanol with loss of water to form [MM'O-6(OCH3)](-) at a rate that was intermediate between those of [M2O6(OH)](-) and [M'O-2(6)(OH)](-). The butylated anions [MM'O-6(OBu)](-) were generated by collisional activation of the ion-pairs Bu4N+[MM'O-7](2-)}(-). Collisional activation of [MM'O-6(OBu)](-) resulted in either the loss of butanal (redox reaction) or the loss of butene (elimination reaction), with the detailed nature of the observations depending on the nature of both M and M'. Selective O-18 labeling indicated that the butoxo ligands of [CrMoO6(OBu)](-) and [CrWO6(OBu)](-) were located on molybdenum and tungsten, respectively. This structural insight allowed a more detailed comparison of reactivity with the homobinuclear species, and highlighted the importance of the neighboring metal center in these reactions.
• Preparation and Characterization of Dinuclear Ni ^II Amine‐Thiophenolate Complexes Coligated by EO ₄ ^– (E = Cl, Re) and EO ₄ ^2– Oxoanions (E = S, Cr, Mo, W)
  作者：Vasile Lozan、Berthold Kersting

  DOI：10.1002/ejic.200700015

  日期：2007.4

  (ReO 4 )][ReO 4 ] (3[ReO 4 ]) , [(L Me )-Ni2(SO 4 )] (4), [(LMe)Ni 2 (CrO 4 )] (5), [(L Me )Ni 2 (MoO 4 )] (6), and [(L Me )Ni 2 (WO 4 )] (7). Complexes 2[ClO 4 ], 3[ReO 4 ], 4, 5, and 7 have been characterized by X-ray crystallography. The complexes are isostructural, with the EO 4 - and EO 4 2- groups bonded in a μ 1,3 -bridging mode to generate dioctahedral N3Ni(p-S)2(μ1,3-EO 4 )NiN3 core structures

  双电荷 EO 4 2- 基团与 [(L Me )-Ni 2 ) 2+ 碎片的相互作用比 EO 4 - 基团更强烈，如 Ni-O 距离所反映的，Ni-O 距离在 2 和 3 中比在 4 中显着更长-7. 4 和 6 中的镍 (II) 离子弱铁磁耦合（分别为 J = 24.8 和 3.75 cm-1），耦合的大小似乎与 Ni-S-Ni 角相关。