| 166906-67-8

• CAS: 166906-67-8
• 化学式: C₁₄H₂₁MoO₄P
• 分子量: 380.232
• InChiKey: YCPAGBYTOIQPND-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

• 作为产物：
  描述：

  、 环戊二烯基钠 以 四氢呋喃 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Formation of Olefins Upon Oxidation of Molybdenum Alkyl Carbynes. Organic Radical Reactivity in an Organometallic Radical Cation

  摘要：

  Decomposition of the complexes (eta(5)-C5H5)(CO){P(OMe)(3)}Mo=CR [R = c-C4H9, (CH2)(3)CH3, and CH(CH2-CH2CH3)(2)] in CHCl3 results in conversion of the carbyne ligand to a terminal olefin. The reaction is initiated by oxidation and occurs during photolysis in CHCl3 or upon slow diffusion of O-2 into the reaction mixtures. Corroborating evidence for initiation of the reaction by electron transfer has been obtained by conversion of the butyl carbyne ligand of (eta(5)-C5H5)(CO){P(OMe)(3)}Mo=C(CH2)(3)CH3 to 1-pentene upon electrochemical oxidation. Mechanistic studies were consistent with H-abstraction by the carbyne radical cation to yield a cationic carbene complex which forms the olefin in a H-shift process. INDO calculations on the carbyne radical cation [(eta(5)-C5H5)(CO){P(OMe)(3)}Mo=CCH2CH3](.+) indicate stabilization upon bending the Mo=C-C angle from 180 degrees to 120 degrees. This change in geometry places spin density on the carbyne carbon in the radical cation although the initial oxidation occurs from an orbital that is primarily nonbonding metal d in character. The oxidized carbyne is thus able to function as a carbon-centered radical and abstract a hydrogen atom at the carbyne carbon. Although the olefin-forming reaction is general far alkyl carbynes with a hydrogen on C2, the tert-butyl carbyne (eta(5)-C5H5)(CO){P(OMe)(3)}Mo=CC(CH3)(3) (2e) did not form an olefin upon oxidation. Instead, photolysis of 2e in CHCl3 yielded the dichloromolybdenum carbyne (eta(5)-C5H5)Cl-2{P(OMe)(3)}Mo=CC(CH3)(3) (5e) via a Cl-abstraction pathway.

  DOI：

  10.1021/ja00129a009