(η(6)-1,4-difluorobenzene)chromium tricarbonyl | 56213-60-6

• 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: (η(6)-1,4-difluorobenzene)chromium tricarbonyl
• 英文别名: (η(6)-1,4-difluorobenzene)Cr(CO)3；(η6-p-F2C6H4)chromium tricarbonyl；(η6-1,4-fluorobenzene)Cr(CO)3
• CAS: 56213-60-6
• 化学式: C₉H₄CrF₂O₃
• 分子量: 250.122
• InChiKey: IIGRTGQONIFMOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1-methyl-ortho-carborane 、 (η(6)-1,4-difluorobenzene)chromium tricarbonyl 在 n-butyl lithium 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以9%的产率得到
  参考文献：
  名称：

  阴离子碳硼烷亲核试剂与铬配位卤代芳烃的反应

  摘要：

  Lithiated C-methyl-o-carborane, LiC2B10H10-(CH3), reacts with the complexes (eta-6-arene)Cr(CO)3 to yield C-methyl-C'-aryl-substituted carboranes. With the complexes (eta-6-o-C6H4X2)Cr(CO)3 the carborane displaces either a hydrogen atom (X = Cl) or a halide (X = F) from the arene ring to give 1-(1'-closo-2'-CH3-1',2'-C2B10H10)2,3-Cl2C6H3 (1) or 1-(1'-closo-2'-CH3-1',2'-C2B10H10)-2-FC6H4 (2), respectively. Reaction of 2 equiv of LiC2B10H10(CH3) with (eta-6-p-C6H4F2)Cr(CO)3 results in the displacement of both fluoride atoms on the arene ring to yield the p-phenylene compound 1,4-(1'-closo-2-CH3-1', 1'-C2B10H10)2C6H4 (3). Compounds 1 and 3 have been characterized by X-ray crystallography. 1 crystallized in the monoclinic space group P2(1) with a = 7.2516 (7), b = 7.7424 (8), and c = 13.4028 (13) angstrom; beta = 97.389 (3)-degrees; V = 750 angstrom3; and Z = 2. Data were collected at 128 K on a modified Picker FACS-1 diffractometer, using Mo K-alpha radiation, to a maximum 2-theta = 50-degrees, giving 1421 unique reflections, and the structure was solved by direct methods. The final discrepancy index was R = 0.038, R(w) = 0.061 for 1355 independent reflections with I > 3-sigma-(I). The C-C bond in the carborane is unusually long, 1.706 (5) angstrom, but it is the shortest interatomic distance within the icosahedron. 3 crystallized in the monoclinic space group P2(1)/n with a 7.024 (1), b = 13.764 (4), and c = 12.335 (4) angstrom; beta = 90.99 (1)-degrees; V = 1192 angstrom3; and Z = 2. Data were collected on a modified Syntex P1BAR diffractometer, using Cu K-alpha radiation, to a maximum 2-theta = 100-degrees, giving 1219 unique reflections, and the structure was solved by direct methods. The final discrepancy index was R = 0.061, R(w) = 0.086 for 1020 independent reflections with I > 2-sigma(I). The molecule is centrosymmetric. The C-C bond in the carborane is rather long, 1.684 (5) angstrom, but it is the shortest interatomic distance in the icosahedron.

  DOI：

  10.1021/om00042a057
• 作为产物：
  描述：

  1,4-二氟苯 、 六羰基铬 以 四氢呋喃 、 二丁醚 为溶剂， 反应 48.0h， 以11%的产率得到(η(6)-1,4-difluorobenzene)chromium tricarbonyl
  参考文献：
  名称：

  正交定向铬芳烃配合物作为对映体特异性C（sp2）–C（sp3）交叉偶联反应的高效介体

  摘要：

  报道了一种新的策略，该策略用于将多种电子多样性的芳族化合物偶联至硼酸酯。偶联顺序依赖于铬芳烃络合物的直接邻位锂化反应，然后形成硼酸酯和氧化反应，具有完全的邻位选择性和对映体特异性，从而以优异的收率和较高的官能团耐受性提供偶联产物。通过X射线，NMR和IR实验对中间体铬芳烃硼酸酯络合物进行了表征，以阐明反应机理。

  DOI：

  10.1002/anie.201711816

文献信息

• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cr: Org.Verb., 1.6.1.2.2.14, page 244 - 249
  作者：

  DOI：——

  日期：——
• Strohmeier, W.; Hellmann, H., Berichte der Bunsen-Gesellschaft
  作者：Strohmeier, W.、Hellmann, H.

  DOI：——

  日期：——
• Heppert, Joseph A.; Morgenstern, Mark A.; Scherubel, Devin M., Organometallics, 1988, vol. 7, # 8, p. 1715 - 1723
  作者：Heppert, Joseph A.、Morgenstern, Mark A.、Scherubel, Devin M.、Takusagawa, Fusao、Shaker, Mohammad R.

  DOI：——

  日期：——
• Strohmeier, W., Zeitschrift fur Naturforschung, 1962, vol. 17 b, p. 627 - 628
  作者：Strohmeier, W.

  DOI：——

  日期：——
• Photochemical Synthesis of (η⁶-Arene)chromium Hydrido Stannyl and (η⁶-Arene)chromium Bis(stannyl) Complexes
  作者：Abbas Khaleel、Kenneth J. Klabunde

  DOI：10.1021/ic951431z

  日期：1996.1.1

  Photolysis of (eta(6)-arene)Cr(CO)(3) complexes and HSnPh(3) in aromatic solvents at room temperature has led to two classes of complexes: hydride stannyl compounds containing the eta(2)-H-SnPh(3) ligand and bis(stannyl) compounds containing two SnPh(3) ligands. The ratio between the two complexes simultaneously produced depends on the choice of the arene. Complexes with different arenes (mesitylene, toluene, benzene, fluorobenzene, and difluorobenzene) have been obtained and characterized including X-ray structures for (eta(6)-C6H3(CH3)(3))Cr(CO)(2)(H)(SnPh(3)) (1a), (eta(6)-C6H3(CH3)(3))Cr(CO)(2)(SnPh(3))(2) (1b), (eta(6)-C6H5F)Cr(CO)(2)(SnPh(3))(2) (4b), and (eta(6)-C6H4F2)Cr(CO)(2)(SnPh(3))(2) (5b). X-ray Crystallography of the last three compounds has given the following results: 1b, monoclinic, space group P2(1)/c (No. 14), a = 13.905(4) Angstrom, b = 18.499(2) Angstrom, c = 17.708(2) Angstrom, Z = 4, V = 4285(1) Angstrom(3); 4b, orthorhombic, space group Pca2(1) (No. 29), a = 16.717(2) Angstrom, b = 18.453(2) Angstrom, c = 25.766(2) Angstrom, Z = 8, V = 7948(2) Angstrom(3); 5b, monoclinic, space group P2(1)/c (No. 14), a = 13.756(2) Angstrom, b = 18.560(2) Angstrom, c = 17.159(2) Angstrom, Z = 4, V = 4372(2) Angstrom(3). The relatively high J(Sn-119-Cr-H) and J(Sn-117-Cr-H) values as well as the X-ray structural data provide evidence for the existence of three-center two-electron bonds in the hydride stannyl complexes. The H-1 NMR data of the complexes are compared with chromium-arene bond distances, and a sensible trend is observed and discussed.