Cp*Re(CO)(PMe3)((15)NN) | 117119-97-8

• 英文名称: Cp*Re(CO)(PMe3)((15)NN)
• CAS: 117119-97-8
• 化学式: C₁₄H₂₄N₂OPRe
• 分子量: 454.531
• InChiKey: DZIYKYKGAXQCBX-WMGQYYDSSA-N

反应信息

• 作为产物：
  描述：

  {Cp*Re(CO)(PMe3)(p-(15)N(α)NC6H4OMe)}{BF4} 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 以82%的产率得到Cp*Re(CO)(PMe3)((15)NN)
  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

文献信息

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

  DOI：——

  日期：——