pentacarbonyltributylstannylmanganese | 54966-76-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: pentacarbonyltributylstannylmanganese
• CAS: 54966-76-6
• 化学式: C₁₇H₂₇MnO₅Sn
• 分子量: 485.046
• InChiKey: LZCNMNJMXHUKGZ-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：

  pentacarbonyltributylstannylmanganese 、 以 氘代苯 为溶剂， 反应 1.0h， 以80%的产率得到(E)-tributyl(dec-1-en-1-yl)stannane
  参考文献：
  名称：

  炔烃氢化锡烷基化中区域选择性的异双金属控制：通过协同 Sn-H 键激活不同合成 α- 和 (E)-β-乙烯基锡烷

  摘要：

  通过可调异双金属 (NHC)Cu-[MCO] 催化剂（[MCO] = FeCp(CO)2 或 Mn(CO)5）协同 Sn-H 键活化氢锡烷 (Bu3SnH) 能够在温和条件下催化氢化锡烷基化末端炔, 马尔科夫尼科夫/反马尔科夫尼科夫选择性由铜/M 配对控制。通过使用MeIMesCu-FeCp(CO)2催化剂，以简单的烷基取代炔烃和Bu3SnH为原料，以高产率和良好的区域选择性制备了多种α-乙烯基锡烷；这些产品在单核金属催化氢化锡烷基化条件下难以获得。此外，在 Cu/Fe 催化条件下，芳基取代的炔烃观察到反向区域选择性，得到 (E)-β-乙烯基锡烷作为主要产物。另一方面，通过使用 IMesCu-Mn(CO)5 催化剂，由伯、仲和叔烷基取代的炔烃制备了多种 (E)-β-乙烯基锡烷，因此证明了由 Cu/Fe 与 Cu/Mn 配对控制的炔烃氢化锡烷基化的不同区域选择性。这两种方法都适用于克级乙烯基

  DOI：

  10.1021/jacs.9b00068
• 作为产物：
  描述：

  sodium-manganese pentacarbonyl 、 三丁基氯化锡 以 四氢呋喃 为溶剂， 生成 pentacarbonyltributylstannylmanganese
  参考文献：
  名称：

  主族-过渡金属键的反应性。第四部分 含有与钼，锰和铁结合的4B族元素的化合物的碘化动力学：结构对反应性的影响

  摘要：

  已经确定了碘在四氯甲烷中与[Fe（cp）（CO）2（MMe 3）]（M = Si，Ge或Sn），[Mo（cp）（CO）3（SnR 3）的反应的速率系数）]（R = Me，Bu或Ph），[Fe（cp）（CO）2（SnR 3）]（R = Me，Bu或Ph），[Mn（CO）5（SnR 3）]（ R = ME等，或C 6 H ^ 11），[锰（CO）5（MME 3）]（M =硅，锗，锡或铅），和[沫（η-C 5 H ^ 4 ME）（CO ）3（SnPh 3）]。4B族元素上的烷基会影响反应活性，这是因为其电子性能而不是其空间效应。当硅被锗，锡和铅替代时，化合物的反应性增加。这是垂直超共轭和MMe 3 +离子（M = Si，Ge，Sn或Pb）的稳定性提高的结果。

  DOI：

  10.1039/dt9760000360

文献信息

• Reactivity of main-group–transition-metal bonds. Part 8. The kinetics of mercuration of compounds containing Group 4B elements bonded to manganese, iron, and molybdenum: effects of structure on reactivity
  作者：John R. Chipperfield、Andy C. Hayter、David E. Webster

  DOI：10.1039/dt9770000921

  日期：——

  The kinetics of cleavage by HgBr2 of the main-group–transition-metal bonds in the following compounds are reported: [Mn(CO)5(MR3)](M = Sn, R = Et, Bun, or C6H11; M = Si or Ge, R = Me); [Fe(cp)(CO)2(MR3)](M = Sn, R = Bun or C6H11; M = Si or Ge, R = Me; cp =η-cyclopentadienyl); and [Mo(cp)(CO)3(SnBun3)Bun3]. The structure–reactivity patterns indicate that mercuration involves an SE2(open) transition

  据报道，以下化合物中HgBr 2的主-过渡金属键裂解的动力学：[Mn（CO）5（MR 3）]（M = Sn，R = Et，Bu n或C 6 H 11； M = Si或Ge，R = Me）；[Fe（cp）（CO）2（MR 3）]（M ＝ Sn，R ＝ Bu n或C 6 H 11； M ＝ Si或Ge，R ＝ Me； cp ＝η-环戊二烯基）；和[Fe（cp）（CO）2（MR 3）] 。和[Mo（cp）（CO）3（SnBu n 3）Bu n 3 ]。结构-反应模式表明汞离子涉及一个S E 2（开放）过渡态。汞（II）溴化物不会裂解[Mn（CO）5（SnPh 3）]或[Fe（cp）（CO）2（SnPh 3）]中的锡-过渡金属键，但会裂解这些化合物中的苯基-锡键。
• Reaktionen von triorganylstannyldiazoessigsäureestern mit Brompentacarbonylmangan
  作者：Helmut Kandler、Henry William Bosch、Valery Shklover、Heinz Berke

  DOI：10.1016/0022-328x(91)86149-k

  日期：1991.5

  Manganese pentacarbonyl bromide reacts with 2 equivalents of alkyl triorganylstannyldiazo acetates 1a-d to form the tetracarbonyl-μ(C,O)(1,2-alkoxycarbonyl-2-triorganylstannylethen-1-yl)manganese compounds 2a-d, presumably via the carbyne intermediate 3. Complex 2d was characterized by an X-ray crystal structure analysis.

  五羰基溴化锰与2当量的烷基三有机基锡烷基重氮乙酸酯1a - d反应形成四羰基-μ（C，O）（1,2-烷氧基羰基-2-三有机基苯乙烯基-1-基）锰化合物2a - d，大概是通过碳炔中级3。配合物2d通过X射线晶体结构分析来表征。
• Reaction of acetyl complexes with HMR3 (M = Si, Sn). Mechanism of acetaldehyde formation
  作者：R. W. Wegman

  DOI：10.1021/om00135a013

  日期：1986.4.1
• Photochemical reaction of dinuclear manganese carbonyl compounds with tributyltin hydride and with silanes
  作者：Richard J. Sullivan、Theodore L. Brown

  DOI：10.1021/ja00024a021

  日期：1991.11

  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.
• 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.