[Mo2Cp2(μ-methoxycarbyne)2(μ-PCy2)]BF4*dichloromethane | 864298-42-0

• 英文名称: [Mo2Cp2(μ-methoxycarbyne)2(μ-PCy2)]BF4*dichloromethane
• 英文别名: [Mo2Cp2(μ-PCy2)(μ-COMe)2]BF4*CH2Cl2
• CAS: 864298-42-0
• 化学式: BF₄*CH₂Cl₂*C₂₆H₃₈Mo₂O₂P
• 分子量: 777.178
• InChiKey: IRYIHWXDDILIPW-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：

  [Mo2Cp2(μ-methoxycarbyne)2(μ-PCy2)]BF4*dichloromethane 、 一氧化碳 以 not given 为溶剂， 生成 [Mo2Cp2(μ-η2:η2-dimethoxyacetylene)(μ-PCy2)(CO)2]BF4
  参考文献：
  名称：

  Formation and Cleavage of C−C, C−O, and O−H Bonds Involving Methoxycarbyne and Hydroxycarbyne Ligands at Unsaturated Dimolybdenum Complexes

  摘要：

  Reversible carbyne-carbyne coupling occurs upon addition of simple ligands L (CO, (BuNC)-Bu-t) to the bis(methoxycarbyne) complex [Mo2Cp2(mu-COMe)(2)-(mu-PCy2)]BF4 to give the dimethoxyacetylene-bridged derivatives [Mo2Cp2{mu-eta(2):eta(2)-C-2(OMe)(2)}(mu-PCy2)L-2]BF4. Upon demethylation, the dicarbonyl cation experiences a 1,2-methoxyl shift to give the carboxycarbyne derivative [Mo2Cp2{mu-C(CO2Me)}(mu-PCy2)(CO)(2)].

  DOI：

  10.1021/om050550b
• 作为产物：
  描述：

  [Mo2Cp2(μ-η2:η2-dimethoxyacetylene)(μ-PCy2)(CO)2]BF4 以 四氢呋喃 为溶剂， 生成 [Mo2Cp2(μ-methoxycarbyne)2(μ-PCy2)]BF4*dichloromethane
  参考文献：
  名称：

  Formation and Cleavage of C−C, C−O, and O−H Bonds Involving Methoxycarbyne and Hydroxycarbyne Ligands at Unsaturated Dimolybdenum Complexes

  摘要：

  Reversible carbyne-carbyne coupling occurs upon addition of simple ligands L (CO, (BuNC)-Bu-t) to the bis(methoxycarbyne) complex [Mo2Cp2(mu-COMe)(2)-(mu-PCy2)]BF4 to give the dimethoxyacetylene-bridged derivatives [Mo2Cp2{mu-eta(2):eta(2)-C-2(OMe)(2)}(mu-PCy2)L-2]BF4. Upon demethylation, the dicarbonyl cation experiences a 1,2-methoxyl shift to give the carboxycarbyne derivative [Mo2Cp2{mu-C(CO2Me)}(mu-PCy2)(CO)(2)].

  DOI：

  10.1021/om050550b

文献信息

• Chemistry of Unsaturated Group 6 Metal Complexes with Bridging Hydroxy and Methoxycarbyne Ligands. 1. Synthesis, Structure, and Bonding of 30-Electron Complexes
  作者：M. Esther García、Daniel García-Vivó、Miguel A. Ruiz、Santiago Alvarez、Gabriel Aullón

  DOI：10.1021/om700562g

  日期：2007.9.1

  30-electron complexes by a configuration of type σ2δ4, with the δ orbitals being involved in π back-bonding to the carbonyl bridges. Upon methylation of the latter ligands, these δ-bonding orbitals become more delocalized over the Mo2C(carbyne) triangle and constitute the π-bonding component of the metal−carbyne bond. Therefore, a partial reduction of the direct metal−metal overlap occurs upon formation

  新的阳离子烷氧基和hydroxycarbyne络合物[M 2的CP 2（μ-COR）（μ-PR ' 2）2 ] BF 4（CP =η 5 -C 5 H ^ 5 ; M = W，R = Me中，R'= pH值; M =钼，R =我和H，R” = ET）和[沫2的CP 2（μ-COR）（μ-COR '）（μ-PCY 2）] BF 4（R =甲基; R'通过相应的中性单羰基前体与[Me 3 O] BF 4或HBF 4 ·OEt 2的反应可以高收率获得= H，Me，Et）。在二氯甲烷中。虽然甲氧基碳炔络合物在室温下稳定，但类似的羟基碳炔化合物是热不稳定的，且高于约。253ķ他们经历氢迁移氧到金属，以得到新的氢化羰基配合物[沫2的CP 2（H）（μ-PET 2）2（CO）] BF 4和[沫2的CP 2（H）（ μ-COME）（μ-PCY 2）（CO）] BF 4作为主要产品。通过密度泛函理论研究了这