| 282726-79-8

• 分子结构分类: 有机化合物
• CAS: 282726-79-8
• 化学式: C₁₇H₁₁ClF₁₀N₃ORe
• 分子量: 684.938
• InChiKey: CQFSKNMLZAURIF-UHFFFAOYSA-M

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

• 作为产物：
  描述：

  [ReOCl₃(PPh₃)₂] 、 N'-methyl-N'-[2-(2,3,4,5,6-pentafluoroanilino)ethyl]-N-(2,3,4,5,6-pentafluorophenyl)ethane-1,2-diamine 在 2,6-lutidine 作用下， 以 乙醇 为溶剂， 以77.6%的产率得到
  参考文献：
  名称：

  Synthesis of Oxorhenium(V) Complexes with Diamido Amine Ancillary Ligands and Their Role in Oxygen Atom Transfer Catalysis

  摘要：

  The detailed syntheses of complexes of the form [Re(O)(X)(RNCH2CH2)(2)N(Me)] (X=Me, Cl, l, R=mesityl, C6F5), 1-3, incorporating diamidoamine ancillary ligands are described. X-ray crystal structures for the complexes [Re(O)(Me)((C6F5)NCH2CH2)(2)N(Me)], 1a, [Re(O)(l)((C6F5)N CH2CH2)(2)N(Me)], 3a, and [Re(O)(l)((Mes)NCH2)(2)N(Me)], 3b, are reported. The geometry about the metal center in la is best described as a severely distorted square pyramid with the oxo ligand in the apical position. In contrast, the geometry about the metal center in 3a is best described as a severely distorted trigonal bipyramid, with the iodo ligand occupying the apical position and the diamido nitrogens and the oxo ligand occupying the equatorial plane. The catalytic activities of these complexes for oxygen atom transfer, OAT, from pyridine-N-oxides, PyO, to PPh3 were also examined. The reactions exhibited a clear dependence on the diamido ligand substituent and the X ligand (Me, l, Cl) attached to the metal, with the combined effect that electron-withdrawing substituents on the diamido ligand and poor or donors directly attached to the metal center increases the rate of catalytic activity. The kinetics of OAT from pyridine-N-oxides to Re were also investigated. The reactions displayed clean first order kinetics in Re and saturation kinetics for the dependence on PyO. Changing the PyO substrate had no effect on the saturation value, k(sat), suggesting that the OAT reaction in these five-coordinate complexes appears to be governed by isomerization of the starting complex. Attempts to isolate a postulated Re(VII) intermediate were not successful because of hydrolytic degradation. The product of hydrolytic degradation [((C6F5)N(H)CH2CH2))(2)NH(Me)][X], (X=ReO4-, or l(-)), 4 can be isolated, and its X-ray crystal structure is reported. Although the Re(VII) intermediate could not be isolated, its activity in OAT reactions was probed by competition experiments with PPh3 and four para-substituted triarylphosphines (p-X-Ph)(3)P (X = OMe, Me, Cl, CF3). These experiments led to a Hammett that yielded a reaction constant of p = -0.30 +/- 0.01. This data suggests a positive charge buildup on phosphorus for the OAT reaction and is consistent with the nucleophilic attack of phosphorus on an electrophillic metal oxo.

  DOI：

  10.1021/ic901434u

文献信息

• Molybdenum, Tungsten, and Rhenium d² Complexes That Contain the [(C₆F₅NCH₂CH₂)₂NMe]²^- Ligand
  作者：Frank V. Cochran、Peter J. Bonitatebus、Richard R. Schrock

  DOI：10.1021/om0001117

  日期：2000.6.1

  The reaction between (C6F5NHCH2CH2)2NH and methyl iodide in the presence of base leads to (C6F5NHCH2CH2)2NMe (H2[ArFNMe]) in good yield. Reactions between H2[ArFNMe] and MCl4 (M = Mo or W) in the presence of NEt3 yield pseudooctahedral paramagnetic compounds of the type [Et3NH][ArFNMe]MCl3}. The reaction between 3 equiv of MeMgCl and [Et3NH][ArFNMe]MoCl3} produced paramagnetic trigonal bipyramidal

  在碱的存在下，（C 6 F 5 NHCH 2 CH 2）2 NH与甲基碘之间的反应以良好的产率得到（C 6 F 5 NHCH 2 CH 2）2 NMe（H 2 [Ar F NMe]）。在NEt 3存在下，H 2 [Ar F NMe]与MCl 4（M = Mo或W）之间的反应产生[Et 3 NH] [Ar F NMe] MCl 3 }型拟八面体顺磁性化合物。3当量的MeMgCl与[Et3 NH] [Ar F NMe] MoCl 3 }产生顺磁三角双锥体[Ar F NMe] MoMe 2。H 2 [Ar F NMe]和Mo（NMe 2）4之间的反应产生的是顺磁七坐标[（C 6 F 4（NMe 2）NCH 2 CH 2）2 NMe] MoF 2，而不是五坐标[[C 6 F 5 NCH 2 CH 2）2 NMe] Mo（NMe 2）2，而H 2 [Ar F NMe]，[NEt 4 ] 2 [Re（O）Cl