dibromo phenyl dimethylphosphorane | 138169-31-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dibromo phenyl dimethylphosphorane
• 英文别名: Dibromo(dimethyl)phenyl-lambda~5~-phosphane；dibromo-dimethyl-phenyl-λ5-phosphane
• CAS: 138169-31-0
• 化学式: C₈H₁₁Br₂P
• 分子量: 297.957
• InChiKey: WALDBGTVBGVDAP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  dibromo phenyl dimethylphosphorane 、 铁粉 以 乙醚 为溶剂， 生成 bis(dimethyl(phenyl)-l5-phosphaneyl)iron(V) bromide
  参考文献：
  名称：

  The reaction of coarse-grain metal powders with phosphoranes: a facile activation of metallic reagents and a novel route to metal–phosphine complexes. The X-ray crystal structures of Mnl₂(PPhMe₂) and FeBr₃(PPhMe₂)₂

  摘要：

  粗颗粒金属粉末和膦烷在二乙醚中的反应为获得新的和现有的过渡金属膦络合物提供了一条途径，例如 Nil3(PMe3)2、FeBr3(PPhMe2)2 和 Mnl2(PPhMe2)。

  DOI：

  10.1039/c39910001447

文献信息

• Inorganic Grignard analogues. Reaction of cobalt powder with triorganodiiodophosphorus compounds to form [PR3I][Co(PR3)I3]. Crystal structure of [PPh3I][Co(PPh3)I3], and isolation of the novel complexes [PPh3I][Co(PPh3)IBr2] and [SbPh3I][Co(SbPh3)I3]
  作者：Stephen M. Godfrey、Helen P. Lane、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1039/dt9930001599

  日期：——

  The reactions of a large number of triorganodiiododophosphorus compounds, R3PI2 [R3 = Et3, Pr(n)3, Bu(n)3, PhMe2, Ph2Me, Ph2Pr(n), Ph3 (o-,m- or p-MeC6H4)Ph2, or (m-MeC6H4)3], with unactivated cobalt metal in dry diethyl ether have been studied. All reactions produce the novel ionic complexes [PR3I][Co(PR3)I3] in quantitative yield, illustrated crystallographically for [PPh3I][Co(PPh3)I3]. However, where R3 = PhMe2 both the ionic complex and the cobalt(III) complex [Co(PPhMe2)2I3] are produced from the same reaction. The previously reported isolation of the 'frozen transition-state complex' [Co(PBun3)3I8] from the reaction of Bun3PI2 with cobalt powder has been reinvestigated; when allowed to proceed to completion, the reaction produces the ionic complex described above. The compound Ph3PIBr reacts with cobalt powder to produce the mixed-halide ionic complex [PR3I][Co(PR3)IBr2]. All the complexes [PR3I][Co(PR3)I3] have been studied using Raman and visible spectroscopy, the latter confirming the tetrahedral geometry of the cobalt anion. Very little reaction is observed with the corresponding dibromophosphorus compounds, R3PBr2, but in some cases visible spectroscopic studies on the trace of complex formed suggest a tetrahedral cobalt(II) species, perhaps similar to the iodo-complexes described above. Additionally, Ph3SbI2 reacts with cobalt metal in an analogous way to Ph3PI2 to produce the novel complex [SbPh3I][Co(SbPh3)I3].
• Inorganic grignard analogues. Reaction of nickel powder with dihalogenotriorganophosphorus compounds to form nickel-(II) and -(III) phosphine complexes; isolation of planar [Ni(PPh3)I3]? and the crystal structure of [Ni(PPhMe2)2Br2]
  作者：Stephen M. Godfrey、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1039/dt9930002875

  日期：——

  Reactions of dihalogenotriorganophosphorus compounds R3PX2 (X = Br or I) with unactivated coarse-grain nickel metal powder have been investigated. The nature of the nickel phosphine complexes formed is remarkably dependent on both R and X. Where R not-equal Me and X = I the nickel(II) complexes [R3PI] [Ni(PR3)I3] are formed, analogous to, but not isostructural with, similar cobalt complexes of the same stoichiometry formed from cobalt powder and R3PI2. Quantitative electronic spectroscopic studies indicated that, surprisingly, the [R3PI][Ni(PR3)I3] complexes all have predominantiy square-planar geometry around nickel. Where R = Me and X = 1, the nickel(III) complex [Ni(PMe3)2I3] is obtained in quantitative yield, the other product being diiodine. Reaction of nickel powder with Me2PhPI2 yields both the nickel(II) complex, [MePhPI][Ni(PPhMe2)I3], and the nickel(III) complex, [Ni(PPhMe2)2I3]. These observations again mirror analogous cobalt reactions. Reaction of the analogous dibromo compounds, R3PBr2, with nickel powder is extremely sensitive to the nature of R. Where R = Me, Et or Pn(n) no reaction occurs; where R3 = PhMe2 the square-planar complex [Ni(PPhMe2)2Br2] and an octahedral complex of stoichiometry Ni(PPhMe2)2Br, are obtained in equal yield. Where R3 = Ph2Pr(n) the octahedral complex [Ni(PPh2Prn)2Br4] is formed with a trace of the planar complex [Ni(PPh2Prn)2Br2], and where R = Ph the octahedral complex [Ni(PPh3)2Br4] is formed in quantitative yield. The complex [Ni(PPhMe2)2Br] has been crystallographically characterised: monoclinic, space group P2(1)/a, a = 10.018(2), b = 10.249(1), c = 10.138(1) angstrom and Z = 2 (molecule centrosymmetric).
• The reaction of bromo- and iodo-phosphoranes with unactivated coarse grain manganese metal powder to yield [MnI₂(phosphine)₂] and [{MnX₂(phosphine)}_n](X = Br or I) by insertion of Mn into the P–X bond. The crystal structure of [MnI₂(PPh₃)₂]
  作者：Stephen M. Godfrey、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1039/dt9930000371

  日期：——

  The novel reaction of crude manganese metal powder with dibromo- and diiodo-phosphoranes, R3PX2, has been studied. Reaction of the phosphoranes R3PI2 (R = phenyl or substituted aryl) with manganese allows insertion of the metal into P-X bonds and gives the monomeric tetrahedral complexes [MnI2(PR3)2] and MnI2. However, reaction of R3PX2 (R3 = mixed aryl/alkyl, trialkyl; X = Br or I) with manganese, whilst once again proceeding via insertion into P-X bonds, now leads to the quantitative isolation of the polymeric complexes [MnX2(PR3)}n], thus illustrating the subtle nature of these reactions. Examples of both types of complex have been crystallographically characterised and represent rare examples of such. There is some evidence that where R3 = Ph2Me an equilibrium exists and both types of complex, [MnI2(PPh2Me)2] and [MnI2(PPh2Me)}n] can be detected from the same reaction.
• Bricklebank, Neil; Godfrey, Stephen M.; McAuliffe, Charles A., Journal of the Chemical Society, Dalton Transactions
  作者：Bricklebank, Neil、Godfrey, Stephen M.、McAuliffe, Charles A.、Molloy, Kieran C.

  DOI：——

  日期：——
• The reaction of coarse-grain metal powders with phosphoranes: a facile activation of metallic reagents and a novel route to metal–phosphine complexes. The X-ray crystal structures of Mnl₂(PPhMe₂) and FeBr₃(PPhMe₂)₂
  作者：Stephen M. Godfrey、David G. Kelly、Anthony G. Mackie、Philomena P. Mac Rory、Charles A. McAuliffe、Robin G. Pritchard、Susan M. Watson

  DOI：10.1039/c39910001447

  日期：——

  A route to new and existing transition metal phosphine complexes is provided by the reaction of coarse-grain metal powders and phosphoranes in diethyl ether, as exemplified here by Nil3(PMe3)2, FeBr3(PPhMe2)2 and Mnl2(PPhMe2).

  粗颗粒金属粉末和膦烷在二乙醚中的反应为获得新的和现有的过渡金属膦络合物提供了一条途径，例如 Nil3(PMe3)2、FeBr3(PPhMe2)2 和 Mnl2(PPhMe2)。