mer-MoBr3(PMe3)3 | 82847-37-8

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: mer-MoBr3(PMe3)3
• CAS: 82847-37-8；131321-24-9
• 化学式: C₉H₂₇Br₃MoP₃
• 分子量: 563.887
• InChiKey: RGMLVUATOPGPMZ-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  6.61
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 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

• 作为反应物：
  描述：

  mer-MoBr3(PMe3)3 、 溴 以 甲苯 为溶剂， 生成 tris(trimethyl-l5-phosphaneyl)molybdenum(VII) bromide
  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
• 作为产物：
  描述：

  MoBr3(THF)3 、 三甲基膦 以 四氢呋喃 为溶剂， 生成 mer-MoBr3(PMe3)3
  参考文献：
  名称：

  Krueger, Steven T.; Poli, Rinaldo; Rheingold, Arnold L., Inorganic Chemistry, 1989, vol. 28, # 26, p. 4599 - 4607

  摘要：

  DOI：

文献信息

• Synthesis of binuclear and trinuclear cluster halides of molybdenum and rhenium, and of carbonyl halides of rhenium, iridium, ruthenium, and platinum using metal atoms
  作者：Paul R. Brown、F. Geoffrey N. Cloke、Malcolm L. H. Green、Robert C. Tovey

  DOI：10.1039/c39820000519

  日期：——

  synthetic precursors; co-condensation of rhenium with oxalyl chloride gives [Re(CO)4Cl]2, ruthenium atoms when co-condensed with oxalyl chloride give a carbonyl halide compound which adds trimethylphosphine forming [Ru(Me3)P3(CO)Cl2], and similarly, iridium atoms with oxalyl chloride and then triphenylphosphine give [Ir(CO)2(PPh3)Cl3].

  诸如1,2-二溴-（或二氯-）乙烷或烯丙基氯之类的反应性卤代烃会在共缩合条件下卤化钼和rh的原子，从而以较低的价态形成溶剂化的过渡金属卤化物，例如[Re 3 Cl 9（THF）3 ]（THF ＝四氢呋喃），它们是有用的合成前体。rh与草酰氯共缩合得到[Re（CO）4 Cl] 2，与草酰氯共缩合时的钌原子得到羰基卤化物，该化合物加三甲基膦形成[Ru（Me 3）P 3（CO）Cl 2 ]，并且类似地，铱原子与草酰氯然后再与三苯膦生成[Ir（CO）2（PPh 3）Cl 3 ]。
• Fettinger, James C.; Gordon, John C.; Mattamana, Sundeep P., Inorganic Chemistry, 1996, vol. 35, # 25, p. 7404 - 7412
  作者：Fettinger, James C.、Gordon, John C.、Mattamana, Sundeep P.、O'Connor, Charles J.、Poli, Rinaldo、Salem, Ghadi

  DOI：——

  日期：——