trans-[PtPhBr(SMe2)2] | 925891-85-6

• 英文名称: trans-[PtPhBr(SMe2)2]
• 英文别名: trans-[PtBr(Ph)(SMe2)2]
• CAS: 925891-85-6
• 化学式: C₁₀H₁₇BrPtS₂
• 分子量: 476.361
• InChiKey: XVQJSGNMVREAJW-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  trans-[PtPhBr(SMe2)2] 、 三苯基膦 以 not given 为溶剂， 生成 trans-(phenyl)bromobis(triphenylphosphine)platinum
  参考文献：
  名称：

  Mechanism of the Competition between Phenyl Insertion and Ligand Reductive Elimination on a Hindered Platinum(IV) Cyclometalated Complex

  摘要：

  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.

  DOI：

  10.1021/om060818e
• 作为产物：
  描述：

  二甲基硫 、 以 not given 为溶剂， 生成 trans-[PtPhBr(SMe2)2]
  参考文献：
  名称：

  Mechanism of the Competition between Phenyl Insertion and Ligand Reductive Elimination on a Hindered Platinum(IV) Cyclometalated Complex

  摘要：

  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.

  DOI：

  10.1021/om060818e

文献信息

• Synthesis, Structure, and Reactivity of Arylchlorobis(dialkyl sulfide)platinum(II) Complexes
  作者：Ola F. Wendt、Åke Oskarsson、Johann G. Leipoldt、Lars I. Elding

  DOI：10.1021/ic970189o

  日期：1997.9.1

  bond-weakening. Comparison of the reaction rates of the present series of complexes with their bis(phosphine) analogues and with related cyclometalated compounds shows that the triethylphosphine complexes are 2-3 orders of magnitude less reactive than the thioether complexes, which in turn are a factor 10-20 less reactive than the cyclometalated ones. This reactivity increase can be rationalized mainly

  已合成反式-[PtRCl（SR'（2））（2）]的配合物，其中R = Ph，甲磺酰基和对茴香基，R'= Me或Et，并确定了它们的晶体和分子结构。反式[PtPhCl（SEt（2））（2）]（2）的晶体是三斜晶（P＆onemacr;），a = 10.112（6）Å，b = 13.158（2）Å，c = 14.714（5）Å alpha = 102.48（2）度，beta = 94.394（4）度，γ= 90.22（3）度，Z =4。反式-[Pt（mesityl）Cl（SMe（2））（2）]的晶体4）是单斜晶（P2（1）/ c），a = 13.158（2）Å，b = 9.170（1）Å，c = 16.013（3）Å，beta = 120.93（2）度，Z = 4，并且[Pt（对茴香基）Cl（SMe（2））（2）]（5）的晶体是单斜晶（P2（1）/ n），a = 9.879（4）Å，b = 8.128（2）Å