(1-propynyl-2-methylene-7,7-dimethylbicyclo[2.2.1]-2-heptane)CoMoCp(CO)5 | 168398-50-3

• 英文名称: (1-propynyl-2-methylene-7,7-dimethylbicyclo[2.2.1]-2-heptane)CoMoCp(CO)5
• CAS: 168398-50-3；168279-39-8
• 化学式: C₂₃H₂₃CoMoO₅
• 分子量: 534.366
• InChiKey: KTWVIVIOPACOFK-BPFNDFOTSA-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：

  四氟硼酸-二乙醚络合物 、 (1-propynyl-2-methylene-7,7-dimethylbicyclo[2.2.1]-2-heptane)CoMoCp(CO)5 以 乙醚 为溶剂， 以75%的产率得到
  参考文献：
  名称：

  A Synthetic and X-Ray Crystallographic Study of Cobalt and Molybdenum Cluster Complexes of the 2-Fenchyl Cation: Metal-Mediated Wagner-Meerwein Rearrangements

  摘要：

  Treatment of 2-exo-propynylfenchol, 4a, with dicobalt octacarbonyl gives the sterically crowded (2-exo-propynylfenchol)Co-2(CO)(6) cluster, 5a. Upon protonation, 5a yields the cobalt-stabilized 2-fenchyl cation 6, which is in equilibrium with its Wagner-Meervein rearranged 2-bornyl isomer, 9, bearing the Co2C2 tetrahedral cluster moiety at the C(1) bridgehead position. Aqueous quenching of the mixture of cations 6 and 9 yields. (2-endo-propynylfenchol)Co-2(CO)(6) 5b, together with two alkenes, 7a and 7b, derived by deprotonation of the 2-bornyl cation 9. Replacement of one Co(CO)(3) vertex in 7a by a (C5H5)Mo(CO)(2) moiety, and subsequent reprotonation, generates the Mo-Co cluster-substituted 2-bornyl cation 19a, which undergoes Wagner-Meerwein rearrangement to the more sterically demanding exo-fenchyl cation 17a. The isomerization. of 19a to 17a is rationalized in terms of the enhanced ability of a (C5H5)Mo(C0)2 cluster vertex, relative to a Co(CO)(3) fragment, to alleviate the electronic deficiency at a cationic center. (2-endo-Propynylfenchol)Co-2(CO)(6), 5b, crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a = 7.408(2) Angstrom, b = 15.750(2) Angstrom, c = 17.598(2) Angstrom, and V = 2052.6(7) Angstrom(3) for Z = 4. [(2-exo-propynylfenchyl)MoCo(CO)(5)(C5H5)] [BF4], 17a, crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a = 12.569(2) Angstrom, b =13.491(6) Angstrom, and c = 141473(3) Angstrom, and V = 2454(1) Angstrom(3) for Z = 4.

  DOI：

  10.1021/ja00131a012
• 作为产物：
  描述：

  cyclopentadienylmolybdenum tricarbonyl dimer 、 (1-propynyl-2-methylene-7,7-dimethylbicyclo[2.2.1]-2-heptane)Co2(CO)6 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 生成 (1-propynyl-2-methylene-7,7-dimethylbicyclo[2.2.1]-2-heptane)CoMoCp(CO)5
  参考文献：
  名称：

  A Synthetic and X-Ray Crystallographic Study of Cobalt and Molybdenum Cluster Complexes of the 2-Fenchyl Cation: Metal-Mediated Wagner-Meerwein Rearrangements

  摘要：

  Treatment of 2-exo-propynylfenchol, 4a, with dicobalt octacarbonyl gives the sterically crowded (2-exo-propynylfenchol)Co-2(CO)(6) cluster, 5a. Upon protonation, 5a yields the cobalt-stabilized 2-fenchyl cation 6, which is in equilibrium with its Wagner-Meervein rearranged 2-bornyl isomer, 9, bearing the Co2C2 tetrahedral cluster moiety at the C(1) bridgehead position. Aqueous quenching of the mixture of cations 6 and 9 yields. (2-endo-propynylfenchol)Co-2(CO)(6) 5b, together with two alkenes, 7a and 7b, derived by deprotonation of the 2-bornyl cation 9. Replacement of one Co(CO)(3) vertex in 7a by a (C5H5)Mo(CO)(2) moiety, and subsequent reprotonation, generates the Mo-Co cluster-substituted 2-bornyl cation 19a, which undergoes Wagner-Meerwein rearrangement to the more sterically demanding exo-fenchyl cation 17a. The isomerization. of 19a to 17a is rationalized in terms of the enhanced ability of a (C5H5)Mo(C0)2 cluster vertex, relative to a Co(CO)(3) fragment, to alleviate the electronic deficiency at a cationic center. (2-endo-Propynylfenchol)Co-2(CO)(6), 5b, crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a = 7.408(2) Angstrom, b = 15.750(2) Angstrom, c = 17.598(2) Angstrom, and V = 2052.6(7) Angstrom(3) for Z = 4. [(2-exo-propynylfenchyl)MoCo(CO)(5)(C5H5)] [BF4], 17a, crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a = 12.569(2) Angstrom, b =13.491(6) Angstrom, and c = 141473(3) Angstrom, and V = 2454(1) Angstrom(3) for Z = 4.

  DOI：

  10.1021/ja00131a012