{Cp*Re(CO)(PMe3)(p-N2C6H4OMe)}{BF4} | 101835-38-5

• 英文名称: {Cp*Re(CO)(PMe3)(p-N2C6H4OMe)}{BF4}
• CAS: 101835-38-5
• 化学式: BF₄*C₂₁H₃₁N₂O₂PRe
• 分子量: 647.475
• InChiKey: CKDBJLMBPWMEAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  {Cp*Re(CO)(PMe3)(p-N2C6H4OMe)}{BF4} 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 以82%的产率得到(η5-C5Me5)Re(CO)(PMe3)N2
  参考文献：
  名称：

  Investigation of the Formation of Ligated Dinitrogen from Rhenium-Bound Aryldiazenide

  摘要：

  Chemical or electrochemical reduction of the cationic rhenium aryldiazenido complexes [Cp'Re(L(1))(L(2))(p-N(2)C(6)H(4)OMe)][BF4] (1b-7b) generates the corresponding neutral dinitrogen complexes 1a-7a of the type Cp'Re(L(1))(L(2))(N-2) ((a) Cp' Cp; L(1) = L(2) = CO (1a); (b) Cp' = Cp*, L(1) = CO, L(2) = PMe(3) (3a) or P(OMe)(3) (4a); and (c) Cp' Cp*, L(1) = L(2) = CO (2a), PMe(3) (5a), dmpe (6a), or P(OMe)(3) (7a)). Evidence is presented in support of a proposed mechanism which involves one-electron reduction of the aryldiazenido complex cation in 1b-7b to the neutral 19-electron intermediate, followed by C-N bond homolysis to give 1a-7a plus the p-methoxyphenyl radical that proceeds to form anisole by hydrogen atom abstraction from the solvent. The cathodic reduction peak potentials observed for 1b-7b, by cyclic voltammetry are increasingly negative in the sequence of coligands (PMe(3))(2) (5b,-1.89 V) > dmpe (6b,-1.74 V) > [P(OMe)(3)](2) (7b,-1.41 V) > (CO)(PMe(3))(3b,-1.24 V) > (CO)[P(OMe)(3)] (4b, -0.98 V) > (CO)(2) (2b,-0.62 V). The value for the dicarbonyl Cp* complex 2b is more negative than for the corresponding Cp complex 1b (-0.46 V). These potentials are a good indication of the success of chemical reduction: all 1b-7b are reduced to 1a-7a by Na/Hg in THF, whereas Cp(2)Co, which has a smaller reduction potential than Na/Hg, only reduces 1b, 2b, and 4b. The reaction of 2b with NaBH4 is shown by full spectroscopic characterization to produce the aryldiazene complex Cp*Re(CO)(2)(p-NHNC(6)H(4)OMe), which is thermally unstable End yields the dinitrogen complex 2a and anisole.

  DOI：

  10.1021/om00010a032
• 作为产物：
  描述：

  {Cp*Re(CO)(NCMe)(p-N2C6H4OMe)}{BF4} 、 三甲基膦 以 丙酮 为溶剂， 以90%的产率得到{Cp*Re(CO)(PMe3)(p-N2C6H4OMe)}{BF4}
  参考文献：
  名称：

  Klahn, A. Hugo; Sutton, Derek, Organometallics, 1989, vol. 8, # 1, p. 198 - 206

  摘要：

  DOI：

文献信息

• Geometrical Isomers of Neutral (Pentamethylcyclopentadienyl)rhenium Complexes Resulting from Different Orientations of a Singly-Bent Aryldiazenido Ligand
  作者：Ariana Garcia-Minsal、Derek Sutton

  DOI：10.1021/om950578v

  日期：1996.1.9

  OMe (5), Ph (7)] are presented and discussed. The spectra of 1 and 3−5 show that at low temperature two isomers are present in each case and that these isomers interconvert on the NMR time scale. The isomers are interpreted to occur because the p-N2C6H4OMe ligand adopts two different orientations where the aryl group is oriented syn to either the X or Y ligand in these chiral complexes of general formula

  Cp * ReH（CO）（p -N 2 C 6 H 4 OMe）（1）和Cp * Re（CH 3）（CO）（p -N 2 C 6 H 4 OMe）的可变1 H NMR光谱（3）和Cp * ReCl（PR 3）（p -N 2 C 6 H 4 OMe）的可变温度31 P 1 H} NMR光谱[R = Me（4），OMe（5），Ph（7）]进行介绍和讨论。1的光谱和3 - 5表明，在低温下的两种异构体中存在的每一种情况下，这些异构体相互转化的NMR的时间尺度。解释出现这些异构体是因为p -N 2 C 6 H 4 OMe配体采用两个不同的方向，其中在这些通式Cp * ReXY（p -N的手性络合物中，芳基与X或Y配体同向取向2 C 6 H 4 OMe）。7中庞大的PPh 3配体导致压倒性地倾向于仅与Cl基团同向取向，因此仅一种可观察到的异构体。这些中性络合物中芳基二氮杂基配体的构象异构化的活化