2-hydroxyphenolate;tetraethylazanium | 79240-57-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2-hydroxyphenolate;tetraethylazanium
• CAS: 79240-57-6
• 化学式: C₆H₅O₂*C₈H₂₀N
• 分子量: 239.358
• InChiKey: NOZVAEDXRMUUFX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.35
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  43.29
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-hydroxyphenolate;tetraethylazanium 在 THF 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 生成 Cr(CO)4(catecholate)(2-)
  参考文献：
  名称：

  Chromium Tricarbonyl Catecholate Derivatives. Structural and Reactivity Studies of "16-Electron" Complexes

  摘要：

  The formally ''16-electron'' chromium tricarbonyl catecholate derivative containing a hydrogen-bonded catechol (1) has been synthesized from the labile ligand displacement reaction of Cr(CO)(5)THF with 2 equiv of the monoprotonated tetraethylammonium salt of catechol in tetrahydrofuran. Complex 2, the catechol-free derivative, has also been obtained by the removal of the free catechol by the addition of NaOMe. Both complexes have been characterized in solution by infrared and C-13 NMR spectroscopies and in the solid-state by X-ray crystallography. Complex 1 crystallizes in the monoclinic space group P2(1)/c with a 17.532(4) Angstrom, b = 10.541-(4) Angstrom, c = 17.356(7) Angstrom, beta = 95.18(3)degrees, V = 3194(2) Angstrom(3), and d(calc) = 1.278 g/cm(3), for Z = 4. Complex 2 crystallizes in the monoclinic space group P2(1)/n with a = 10.068(8) Angstrom, b = 20.97(2) Angstrom, c = 12.933(9) Angstrom, beta = 94.58(6)degrees, V = 2722(4) Angstrom(3), and d(calc) = 1.233 g/cm(3), for Z = 4, from CH3CN/toluene/THF. The coordination geometry of the dianion in each case is intermediate between square pyramidal and trigonal bipyramidal, with average Cr-O bond lengths of 2.021[3] and 1.998[9] Angstrom, respectively. Hence, the electronic unsaturation of the chromium center is mitigated in part by pi-donation from the catecholate. This phenomenon is enhanced in the absence of intermolecular hydrogen bonding. Evidence for an increase in the pi-donating ability of the catecholate ligand when it is not involved in hydrogen-bonding with an added proton donor, such as catechol or methanol, is noted in solution by infrared and C-13 NMR spectroscopies. That is, in this instance the v(CO) vibrations occur at lower frequences and the C-13 CO resonances are shifted downfield. Both complexes 1 and 2 are unreactive toward good donor ligands such as PMe(3); however, they react to varying extents with P(OMe)(3) and CO, with complex 1 being more reactive.

  DOI：

  10.1021/ic00122a026

文献信息

• Darensbourg, Donald J.; Klausmeyer, Kevin K.; Mueller, Brian L., Angewandte Chemie, 1992, vol. 104, p. 1501 - 1503
  作者：Darensbourg, Donald J.、Klausmeyer, Kevin K.、Mueller, Brian L.、Reibenspies, Joseph H.

  DOI：——

  日期：——