| 136660-36-1

• CAS: 136660-36-1
• 化学式: C₂₈H₅₅MnO₄Sn₂
• 分子量: 748.1
• InChiKey: PDFMJRDKURYRBB-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：
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• 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：

  Hydromanganese pentacarbonyl 、 三正丁基氢锡 以 正己烷 为溶剂， 生成
  参考文献：
  名称：

  Photochemical reaction of dinuclear manganese carbonyl compounds with tributyltin hydride and with silanes

  摘要：

  The photochemical reactions of Mn2(CO)8L2 (L = CO, PMe3, P(n-Bu)3, P(i-Pr)3) with HSnBu3 or HSiEt3 in hexane solutions have been studied, using 366- or 313-nm irradiation, and under CO or Ar atmospheres. Under CO, 1.1-3.7 atm, the products of the reaction of Mn2(CO)10 with HSnBu3 are HMn(CO)5 and Bu3SnMn(CO)5. Under Ar or low CO pressures, a third product, assigned as HMn(CO)4(SnBu3)2, is formed at the expense of Bu3SnMn(CO)5. For a given photon flux, the reaction rate is inversely related to [CO]. The behavior of the system is consistent with a reaction pathway that involves oxidative addition of the hydride to the coordinatively unsaturated metal center formed upon CO loss. Analogous results are observed for the phosphine-substituted manganese carbonyl dimers. Reaction with HSiEt3 proceeds much more slowly under equivalent conditions of irradiation. In the reaction with Mn2(CO)10, only HMn(CO)5 is seen as a significant product, with trace amounts of Et3SiMn(CO)5 also observed. These results are also consistent with oxidative addition to the Co-loss product as the only pathway for the photochemical reaction. None of the manganese dimers undergo photochemical reaction with either fluorene or triphenylmethane, in spite of the comparatively low C-H bond energy in each case.

  DOI：

  10.1021/ja00024a021

文献信息

• Flash photolysis studies of the reactions of dinuclear manganese carbonyl compounds with tributyltin hydride and triethylsilane
  作者：Richard J. Sullivan、Theodore L. Brown

  DOI：10.1021/ja00024a022

  日期：1991.11

  The reactions of Mn2(CO)8L2 (L = CO, PMe3, P(n-Bu)3, P(i-Bu)3, P(i-Pr)3, P(C6H11)3) With HSnBu3 and of Mn2(CO)10 with HSiEt3 were studied via flash photolysis, employing a conventional xenon flash lamp apparatus. The flash photolysis results are consistent with the conclusions based on continuous photolysis studies. The predominant reaction involves oxidative addition of the hydride to manganese at the site of CO loss. The rate of oxidative addition decreases as the steric requirements of L increase. Following oxidative addition, reductive elimination occurs. For HSnBu3, HMn(CO)4L and Bu3SnMn(CO)3L are formed. In the reaction of HSiEt3 with Mn2(CO)10, reformation of HSiEt3 dominates over formation of HMn(CO)5. The lifetime of the intermediate product resulting from the initial addition varies greatly with L. For small L, such as CO or PMe3, the intermediate persists for several seconds. With increasing size of L the addition process is slowed and the rate of elimination increases. A complete model for the reaction systems takes account of the semibridging form of the CO-loss product as the prevalent species in a noncoordinating solvent. Detailed modeling of the reaction system indicates that the on-off equilibrium involving coordination of the semibridging CO to the vacant manganese site is kinetically important. Formation of the semibridging form from the open form appears to have a significant energy barrier.