iodotrimethylphosphonium tetraiodobis(trimethyl-l5-phosphaneyl)molybdate(V) | 852312-39-1

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: iodotrimethylphosphonium tetraiodobis(trimethyl-l5-phosphaneyl)molybdate(V)
• CAS: 852312-39-1
• 化学式: C₃H₉IP*C₆H₁₈I₄MoP₂
• 分子量: 958.697
• InChiKey: CZRKMCLVQJQRCU-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  -7.03
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  mer-MoI3(PMe3)3 、 碘 以 甲苯 为溶剂， 生成 iodotrimethylphosphonium tetraiodobis(trimethyl-l5-phosphaneyl)molybdate(V)
  参考文献：
  名称：

  The Radical Trap in Atom Transfer Radical Polymerization Need Not Be Thermodynamically Stable. A Study of the MoX₃(PMe₃)₃ Catalysts

  摘要：

  The molybdenum(lll) coordination complexes MoX3(PMe3)(3) (X = CI, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of AI(OPri)(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammograrn Of MoX3(MAe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order CI < Br < I) for the one-electron oxidation wave. Addition of X- changes the voltammogram, indicating the formation of MoX4(PMe3)3 for X = Cl and Br. On the other hand, I- is more easily oxidized than the Mol(3)(PMe3)(3) complex; thus, the putative M-4(PMe3)(3) complex is redox unstable. Electrochemical studies Of Mol(3)(PMe3)(3) in the presence of X- (X = Cl or Br) reveal the occurrence of facile halide-exchange processes, leading to the conclusion that the Mol(3)X(PMe3)(3) products are also redox unstable. The oxidation Of MoX3(PMe3)(3) with (1)/Br-2(2) yields MOX3Br(PMe3)(3) (X = Cl, Br), whose molecular nature is confirmed by single-crystal X-ray analyses. On the other hand, the oxidation Of Mol(3)(PMe3)(3) by 12 slowly yields a tetraiodomolybdate(III) salt of iodotrimethylphosphonium, [Me(3)Pl][Mol(4)(PMe3)(3)], as confirmed by an X-ray study. This product has no controlling ability in radical polymerization. The redox instability of Mol3X(PMe3)3 can be reconciled with its involvement as a radical trapping species in the Mol(3)(PMe3)(3)-catalyzed ATRP, given the second-order nature of its decomposition rate.

  DOI：

  10.1021/ja043078e