RhMn(CO)3(μ-η(1):η(2)-CCHC(O)Me) | 164020-06-8

• 英文名称: RhMn(CO)3(μ-η(1):η(2)-CCHC(O)Me)
• CAS: 164020-06-8
• 化学式: C₅₇H₄₈MnO₄P₄Rh
• 分子量: 1078.74
• InChiKey: BXZONCKNMFGFTM-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：

  RhMn(CO)3(μ-η(1):η(2)-CCHC(O)Me) 、 三氟甲烷磺酸甲酯 以 二氯甲烷 为溶剂， 以84%的产率得到[RhMn(μ-η(1):η(1)-MeC=CHC(O)Me)(Ph2PCH2PPh2)2]OSO2CF3
  参考文献：
  名称：

  Bridging Vinylidene Complexes of RhMn and Evidence for Migratory Insertions To Give Terminal Vinyl Groups

  摘要：

  The reaction of the heterobinuclear complex [RhMn(CO)(4)(dppm)(2)] (1) (dppm = Ph(2)PCH(2)PPh(2)) with 3-butyn-2-one at -40 degrees C yields the alkyne-bridged product [RhMn(CO)(4)(mu-HC2C(O)Me)(dppm)(2)] (3), which undergoes a 1,2-hydrogen shift, yielding two isomers of the vinylidene-bridged species [RhMn(CO)(4)(mu-CC)(H)C(O)Me)(dppm)(2)] (4) as the temperature is raised. Compound 4 undergoes facile CO loss to give [RhMn(CO)(3)(CO)(3)(mu-eta(1):eta(2)-CC(H)C(O)Me)(dppm)(2)] (5) in which the ketonic moiety of the bridging vinylidene group coordinates to Mn, filling the open coordination site left vacant by the departing CO. Protonation of the alkyne- or vinylidene-bridged species 3-5 yields a series of vinyl complexes. Addition of methyl triflate to 4 and 5 yields the respective methyl-substituted vinyl complexes, analogous to the protonation products. In the alkylation of 5 at low temperature an intermediate, [RhMn(CH3)(CO)(3)(mu-eta(1):eta(2)-CC(H)C(O)Me)(dppm)(2)][SO3CF3 (12), having a vinylidene bridge and a methyl group terminally bound to Rh, is obtained. The rearrangement of 12 to a vinyl complex upon warming presents evidence for a migratory insertion involving these groups. The structure of 5 was determined by X-ray crystallography. This compound crystallizes in the monoclinic space group P2(1)/n (nonstandard setting of P2(1)/c [No. 14]) with a = 14.489(1) Angstrom, b = 15.754(2) Angstrom, c = 24.104(2) Angstrom,beta = 91.41(1) Angstrom, V = 5500(1) Angstrom(3), and Z = 4. On the basis of 3980 observations the structure has refined to R = 0.058 and R(w) = 0.063.

  DOI：

  10.1021/om00005a039
• 作为产物：
  描述：

  、 3-丁炔-2-酮 以 四氢呋喃 为溶剂， 以90%的产率得到RhMn(CO)3(μ-η(1):η(2)-CCHC(O)Me)
  参考文献：
  名称：

  Bridging Vinylidene Complexes of RhMn and Evidence for Migratory Insertions To Give Terminal Vinyl Groups

  摘要：

  The reaction of the heterobinuclear complex [RhMn(CO)(4)(dppm)(2)] (1) (dppm = Ph(2)PCH(2)PPh(2)) with 3-butyn-2-one at -40 degrees C yields the alkyne-bridged product [RhMn(CO)(4)(mu-HC2C(O)Me)(dppm)(2)] (3), which undergoes a 1,2-hydrogen shift, yielding two isomers of the vinylidene-bridged species [RhMn(CO)(4)(mu-CC)(H)C(O)Me)(dppm)(2)] (4) as the temperature is raised. Compound 4 undergoes facile CO loss to give [RhMn(CO)(3)(CO)(3)(mu-eta(1):eta(2)-CC(H)C(O)Me)(dppm)(2)] (5) in which the ketonic moiety of the bridging vinylidene group coordinates to Mn, filling the open coordination site left vacant by the departing CO. Protonation of the alkyne- or vinylidene-bridged species 3-5 yields a series of vinyl complexes. Addition of methyl triflate to 4 and 5 yields the respective methyl-substituted vinyl complexes, analogous to the protonation products. In the alkylation of 5 at low temperature an intermediate, [RhMn(CH3)(CO)(3)(mu-eta(1):eta(2)-CC(H)C(O)Me)(dppm)(2)][SO3CF3 (12), having a vinylidene bridge and a methyl group terminally bound to Rh, is obtained. The rearrangement of 12 to a vinyl complex upon warming presents evidence for a migratory insertion involving these groups. The structure of 5 was determined by X-ray crystallography. This compound crystallizes in the monoclinic space group P2(1)/n (nonstandard setting of P2(1)/c [No. 14]) with a = 14.489(1) Angstrom, b = 15.754(2) Angstrom, c = 24.104(2) Angstrom,beta = 91.41(1) Angstrom, V = 5500(1) Angstrom(3), and Z = 4. On the basis of 3980 observations the structure has refined to R = 0.058 and R(w) = 0.063.

  DOI：

  10.1021/om00005a039