| 457057-51-1

• CAS: 457057-51-1
• 化学式: C₂₂H₂₂BrNPtS
• 分子量: 607.473
• InChiKey: WEHODRRVJLMMCY-SPLZJOKXSA-M

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：

  、 三苯基膦 以 not given 为溶剂， 生成
  参考文献：
  名称：

  在环金属化的二苯基铂（IV）配合物中意外的形式芳基插入：结构表征的第一个七元环金属化的铂化合物

  摘要：

  通过在[Pt II（Ph）2（SMe 2）2 ]上氧化加成（2-BrC 6 H 4）CHNBzl亚胺的环金属化反应生成相应的[Pt IV Br（Ph）2（C C 5 H 3 CH N已经获得了Bzl）（SMe 2）]化合物，并且已经确定了其三苯基膦衍生物的X射线晶体结构。SMe 2配体在该配合物中的不稳定性使得能够还原性消除C 6 H 6。 分子和另一个苯基配体在环金属化的Pt-C键中的正式插入，产生了第一个结构上具有特征的七元环金属化的铂配合物。

  DOI：

  10.1021/om020260k
• 作为产物：
  描述：

  以 not given 为溶剂， 生成
  参考文献：
  名称：

  在环金属化的二苯基铂（IV）配合物中意外的形式芳基插入：结构表征的第一个七元环金属化的铂化合物

  摘要：

  通过在[Pt II（Ph）2（SMe 2）2 ]上氧化加成（2-BrC 6 H 4）CHNBzl亚胺的环金属化反应生成相应的[Pt IV Br（Ph）2（C C 5 H 3 CH N已经获得了Bzl）（SMe 2）]化合物，并且已经确定了其三苯基膦衍生物的X射线晶体结构。SMe 2配体在该配合物中的不稳定性使得能够还原性消除C 6 H 6。 分子和另一个苯基配体在环金属化的Pt-C键中的正式插入，产生了第一个结构上具有特征的七元环金属化的铂配合物。

  DOI：

  10.1021/om020260k

文献信息

• Kinetico-mechanistic studies on the formation of seven-membered [C,N]-platinacycles: the effect of methyl or fluoro substituents on the aryl ancillary ligands
  作者：Margarita Crespo、Mercè Font-Bardia、Manuel Martínez

  DOI：10.1039/c5dt01926e

  日期：——

  The rate determining step for the formation of seven-membered platinacycles from cyclometallated Pt(iv) aryl complexes is determined by the nature of the substituents on the aryl groups.

  形成七元铂环化合物的速率决定步骤取决于芳基配合物中芳基基团的取代基性质。
• Mechanism of the Competition between Phenyl Insertion and Ligand Reductive Elimination on a Hindered Platinum(IV) Cyclometalated Complex
  作者：Carlos Gallego、Manuel Martínez、Vicent Sixte Safont

  DOI：10.1021/om060818e

  日期：2007.1.1

  Careful tuning of the reaction conditions has been proved to be essential for the operation of two disjunctive reaction mechanisms occurring on the ortho-metalated platinum compounds [(PtBr)-Br-IV(Ph)(2)(C(5)CH(4)CHNZ)(SMe2)] (Z = Me, Bzl, CH2(2,4,6-Me3C6H2)). In dilute solutions, where the already established lability of the SMe2 ligand favors the existence of the pentacoordinated (PtBr)-Br-IV(Ph)(2)(C(4)CH(4)CHNZ)} species, the complex evolves to produce the insertion of one of the phenyl ligands into the cyclometalated Pt-IV-C bond to yield the complexes [(PtBr)-Br-II(C(4)CH(3)C(6)H(4)CHNZ)(SMe2)], which contain a seven-membered cyclometalated ring. The process involves the formation of an hydride intermediate, which has been detected via low-temperature proton NMR for Z = Bzl, prior to the reductive elimination of benzene. In more concentrated solutions, or in the presence of large amounts (200-500 fold) of SMe2, the existence of pentacoordinated species is reduced to a minimum and a reductive C-C coupling takes place between the metalated imine carbon and one of the phenyl ligands, yielding the coordination complexes [(PtBr)-Br-II(Ph)(C(6)H(3)C(6)H(4)CHNZ)(SMe2)], which evolve rapidly to trans-[(PtBr)-Br-II(Ph)(SMe2)(2)] and free C(5)H(3)C(6)H(4)CHNZ. The validity of the mechanisms proposed has been proved via stoichiometric and reactivity studies carried out under carefully controlled conditions, both on initial Pt-IV complex and on the final inserted complex, [(PtBr)-Br-II(C(4)CH(3)C(6)H(4)CHNZ)(SMe2)]. The overall reactivity is rather surprising, given the generally accepted dissociative processes involved in the preliminary steps of reductive elimination reactions on Pt-IV complexes. DFT calculations have been carried out in order to check the energetic validity of the proposed disjunctive reaction mechanisms. From the data obtained, it is clear that the formation of the pentacoordinated species (PtBr)-Br-IV(Ph)(2)(C(5)CH(4)CHNZ)} could effectively lead to the standard C-C reductive coupling, but in our case the existence of the parallel insertion process is highly favored. As a consequence the observed reductive elimination reaction can only occur via the otherwise less favored direct C-C coupling on the octahedral [(PtBr)-Br-IV(Ph)(2)(C(4)CH(4)CHNZ)(SMe2)] starting material.