cis,mer-Mn(CO)2(η(3)-Ph2P(CH2)2P(Ph)(CH2)2PPh2)Br | 186708-43-0

• 英文名称: cis,mer-Mn(CO)2(η(3)-Ph2P(CH2)2P(Ph)(CH2)2PPh2)Br
• 英文别名: cis,mer-Mn(CO)2(η(3)-(Ph2P(CH2)2)2PPh)Br；cis,fac-Mn(CO)2(η(3)-Ph2P(CH2)2P(Ph)(CH2)2PPh2)Br；cis,fac-Mn(CO)2(η(3)-(Ph2P(CH2)2)2PPh)Br
• CAS: 186708-43-0；186708-47-4；33846-34-3；38100-09-3
• 化学式: C₃₆H₃₃BrMnO₂P₃
• 分子量: 725.42
• InChiKey: HKGAXBHSONKMDC-UHFFFAOYSA-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：

  cis,mer-Mn(CO)2(η(3)-Ph2P(CH2)2P(Ph)(CH2)2PPh2)Br 以 solid 为溶剂， 生成 trans-Mn(CO)2(η(3)-Ph2P(CH2)2P(Ph)(CH2)2PPh2)Br(1+)
  参考文献：
  名称：

  Voltammetric, Specular Reflectance Infrared, and X-ray Electron Probe Characterization of Redox and Isomerization Processes Associated with the [Mn(CO)₂(η³-P₂P‘)Br]^+/0 (P₂P‘ = {Ph₂P(CH₂)₂}₂PPh), [Mn(CO)₂(η³-P₃P‘)Br]^+/0 (P₃P‘ = {Ph₂PCH₂}₃P), and [{Mn(CO)₂(η²-dpe)Br}₂(μ-dpe)]^2+/0 (dpe = Ph₂P(CH₂)₂PPh₂) Solid State Systems

  摘要：

  Extremely well defined voltammetric responses are obtained for both oxidation of microcrystalline mononuclear trans- and cis,mer-Mn(CO)(2)(eta(3)-P2P')Br (P2P' = {Ph2P(CH2)(2)}(2)PPh) and cis,mer-Mn(CO)(2)(eta(3)-P3P')Br (P3P' = {Ph2PCH2}(3)P) and binuclear cis,fac-{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe) (dpe = Ph2P(CH2)(2)PPh2) and reduction of cationic trans-[Mn(CO)(2)(eta(3)-P2P')Br]BF4, trans-[Mn(CO)(2)(eta(3)-P3P')Br]BF4, and trans-[{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)](BF4)(2) when they are attached to a graphite electrode and placed in water containing either 0.1 M NaCl or KCl as the electrolyte. The combination of access to species in different oxidation states and different isomeric forms, as well as mononuclear and binuclear species, enables the rates of isomerization and the extent of electronic communication between the metal centers to be evaluated in the solid state and compared to data in organic solvent systems previously reported. The voltammetric data, combined with specular reflectance IR and X-ray electron probe data, established that the following processes occur at the graphite electrode-microcrystal-water (electrolyte) interface (subscript ''s'' denotes solid): trans-Mn(CO)(2)(eta(3)-P2P')Br-s + Cl- reversible arrow trans-[Mn(CO)(2)(eta(3)-P2P')Br]Cl-s + e(-); cis,mer-Mn(CO)(2)(eta(3)-P2P')Br-s + Cl- reversible arrow cis,mer-[MN(CO)(2)(eta(3)-P2P')Br]Cl-s + e(-) --> trans-[Mn(CO)(2)(eta(3)-P2P')Br]Cl-s; trans-Mn(CO)(2)(eta(3)-P3P')Br-s + Cl- reversible arrow trans-[Mn(CO)(2)(eta(3)-P3P')Br]Cl-s + e(-); cis,mer-Mn(CO)(2)(eta(3)-P3P')Br-s + Cl- reversible arrow cis,mer-[Mn(CO)(2)(eta(3)-P3P')Br]Cl-s + e(-) --> trans-[Mn(CO)(2)(eta(3)-P3P')Br]Cl-s; trans-{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)(s) + 2Cl(-) reversible arrow trans-[{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)]Cl-2 s + 2e(-); cis,fac-{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)(s) + 2 Cl- reversible arrow cis,fac-[{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)]Cl-2 s + 2e(-) --> trans-[{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)]Cl-2 s. The reaction pathways in organic solvents are generally analogous. However, the rates of isomerization are slower in the solid state, and shapes of voltammograms and potentials differ significantly.Interestingly, in the binuclear [{Mn)CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)](2+/0) system, no intermediate [{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)](+) species are observed in the solid state, implying that the metal centers are oxidized or reduced at the same potentials, unlike the case in the solution phase, where the [{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)](2+/+) and [{Mn(CO)(2)(eta(2)-dpe)Br}(2)(mu-dpe)](+/0) redox couples are well separated. This result implies that no significant communication occurs between the metal centers in the solid state redox processes.

  DOI：

  10.1021/om970468j
• 作为产物：
  描述：

  五羰基溴化锰(I) 、 双(2-二苯基膦乙基)苯基磷 以 xylene 为溶剂， 生成 cis,mer-Mn(CO)2(η(3)-Ph2P(CH2)2P(Ph)(CH2)2PPh2)Br
  参考文献：
  名称：

  富含异构体的[M（CO）（2）（P（2）P'）X]（+ / 0）的合成，光谱和电化学研究（M = Mn，Re; X = Cl，Br; P（ 2）P'= eta（3）-Ph（2）P（CH（2））（2）P（Ph）（CH（2））（2）PPh（2））系统：新型对的结构表征，mer-Re（CO）（2）（P（2）P'）Cl的非对映异构体的合成。

  摘要：

  Mn（CO）（5）X（X = Cl，Br）与Ph（2）P（CH（2））（2）P（Ph）（CH（2））（2）PPh（2）的反应（ P（2）P'）在回流的二甲苯中导致形成异构纯的顺式，mer-Mn（CO）（2）（eta（3）-P（2）P'）X。二氯甲烷（0.1 M Bu（4）NPF（6））中的循环伏安图显示可逆的单电子氧化（过程1，E（1/2）= 0.142 V）得到顺式，mer- [Mn（CO）（2 ）（P（2）P'）X]（+）。但是，在室温下的丙酮（0.1 M Bu（4）NPF（6））中，过程1是不可逆的，并且观察到另外的氧化还原过程4（E（1/2）= 0.048 V）。在低温下未观察到过程4，而在丙酮中较高的温度下，它与过程1合并，并且还会出现新的可逆氧化还原对（过程5，E（1/2）= -0.411 V）。电解，化学氧化和随后的还原相结合，结合IR和（31）P NMR光谱学和电喷雾质谱（

  DOI：

  10.1021/ic961295d