AsMe3I2 | 17756-08-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: AsMe3I2
• 英文别名: trimethylarsine diiodide；diiodotrimethylarsine；Arsorane, diiodotrimethyl-；diiodo(trimethyl)-λ5-arsane
• CAS: 17756-08-0
• 化学式: C₃H₉AsI₂
• 分子量: 373.835
• InChiKey: KFCVUWGJSSIUMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.14
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  diiron nonacarbonyl 、 AsMe3I2 以 乙醚 为溶剂， 以99%的产率得到iodotrimethylarsonium triiodo(trimethyl-l5-arsaneyl)ferrate(III)
  参考文献：
  名称：

  Reactions of dihalogenotriorgano-phosphorus, -arsenic and -antimony compounds with [Fe₂(CO)₉]. Single-crystal structures of the iron(III) complexes [(Ph₃PO)₂H][FeBr₄] and [Ph₄Sb][Fel₄]·Ph₃Sbl₂and of [Fe(CO)₃(Ph₃P)₂]

  摘要：

  The reaction of [Fe2(CO)9] with compounds of stoichiometry R3EX2 [R3E = Ph3P, (p-MeOC6H4)3P, Me2PhP, Me3As or Ph3Sb, X = I; R3E = Ph3P, Ph3As or Me3As, X = Br] has been investigated and shown to yield diverse products. A series of complexes with the ionic structure [R3EX][Fe(R3E)X3] [E = P, R3 = Ph3, Me2Ph or (p-MeOC6H4)3, X = I; R3E = Me3As; X = I or Br] has been obtained. The reaction of [Fe2(CO)9] with Ph3PBr2 and Ph3AsBr2, however, resulted in the formation of the iron(III) complexes [(Ph3E)2Br][FeBr4]. Hydrolysis of [(Ph3P)2Br][FeBr4] by trace quantities of water produces [(Ph3PO)2H][FeBr4], the crystal structure of which has been determined. Triphenylantimony diiodide reacted with [Fe2(CO)9] yielding the surprising ionic adduct [Ph4Sb][FeI4].Ph3SbI2, remarkable not only for the phenyl migration at the antimony atom, but also for the formation of the rare [FeI4]- anion from a zerovalent iron carbonyl complex. The reaction of [Fe2(CO)9] with the milder diphosphine tetraiodide, I2Ph2PCH2CH2PPh2I2, produced [Fe(CO)3(Ph2PCH2CH2PPh2)I][I3], a complex in which three CO ligands are retained.

  DOI：

  10.1039/dt9940003249
• 作为产物：
  描述：

  三甲基胂 在 碘 作用下， 以 乙醚 为溶剂， 反应 24.0h， 生成 AsMe3I2
  参考文献：
  名称：

  Reactions of dihalogenotriorgano-phosphorus, -arsenic and -antimony compounds with [Fe₂(CO)₉]. Single-crystal structures of the iron(III) complexes [(Ph₃PO)₂H][FeBr₄] and [Ph₄Sb][Fel₄]·Ph₃Sbl₂and of [Fe(CO)₃(Ph₃P)₂]

  摘要：

  The reaction of [Fe2(CO)9] with compounds of stoichiometry R3EX2 [R3E = Ph3P, (p-MeOC6H4)3P, Me2PhP, Me3As or Ph3Sb, X = I; R3E = Ph3P, Ph3As or Me3As, X = Br] has been investigated and shown to yield diverse products. A series of complexes with the ionic structure [R3EX][Fe(R3E)X3] [E = P, R3 = Ph3, Me2Ph or (p-MeOC6H4)3, X = I; R3E = Me3As; X = I or Br] has been obtained. The reaction of [Fe2(CO)9] with Ph3PBr2 and Ph3AsBr2, however, resulted in the formation of the iron(III) complexes [(Ph3E)2Br][FeBr4]. Hydrolysis of [(Ph3P)2Br][FeBr4] by trace quantities of water produces [(Ph3PO)2H][FeBr4], the crystal structure of which has been determined. Triphenylantimony diiodide reacted with [Fe2(CO)9] yielding the surprising ionic adduct [Ph4Sb][FeI4].Ph3SbI2, remarkable not only for the phenyl migration at the antimony atom, but also for the formation of the rare [FeI4]- anion from a zerovalent iron carbonyl complex. The reaction of [Fe2(CO)9] with the milder diphosphine tetraiodide, I2Ph2PCH2CH2PPh2I2, produced [Fe(CO)3(Ph2PCH2CH2PPh2)I][I3], a complex in which three CO ligands are retained.

  DOI：

  10.1039/dt9940003249

文献信息

• Reaction of R3AsI2(R = Me or Et) with zinc metal powder to produce ZnI2(AsMe3)2 and [ZnI2(AsEt3)]2, the first tertiary arsine complexes of zinc(II)
  作者：Stephen M. Godfrey、Charles A. McAuliffe、Robin G. Pritchard、Joanne M. Sheffield

  DOI：10.1039/dt9960003309

  日期：——

  The reaction of Et3AsI2 with zinc metal powder produced the dimeric complex [ZnI2(AsEt3)]2, whereas that of Me3AsI2 gave equimolar quantities of ZnI2(AsMe3)2 and ZnI2, the latter being identified by X-ray powder diffraction. Both arsine complexes have been structurally characterised and as such represent the only examples for zinc(II). A structural change is thus seen on changing the R groups on the R3AsI2 compound. The complex ZnI2(AsMe3)2 represents the sole example of a bis(ligand) complex of zinc(II) containing a Group 15 donor atom. Both complexes contain the zinc atoms in essentially tetrahedral geometry but significant distortion is noted for ZnI2(AsMe3)2, which may be the result of unfavourable steric interactions.

  Et3AsI2 与锌金属粉末的反应生成了二聚体配合物 [ZnI2(AsEt3)]2，而 Me3AsI2 的反应则得到了等摩尔的 ZnI2(AsMe3)2 和 ZnI2，后者通过 X 射线粉末衍射法确认。两个砷烷配合物已被结构表征，因此它们代表了锌(II) 的唯一例子。通过改变 R3AsI2 化合物中的 R 取代基，观察到了结构变化。配合物 ZnI2(AsMe3)2 是含有第 15 族供体原子的锌(II) 双配体配合物的唯一例子。两个配合物中的锌原子基本上呈四面体几何形状，但 ZnI2(AsMe3)2 显示出显著的畸变，这可能是由于不利的立体相互作用所致。
• Facile synthesis of a rare example of an iron(III) iodide complex, [FeI3(AsMe3)2], from the reaction of Me3AsI2 with unactivated iron powder
  作者：Nicholas A. Barnes、Stephen M. Godfrey、Nicholas Ho、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1016/j.poly.2013.02.066

  日期：2013.5

  Abstract The reaction of Me3AsI2 with unactivated iron powder provides a synthetic entry into the coordination chemistry of iron(III) iodide, which is inaccessible by traditional routes due to the low stability of the parent halide FeI3. The reaction of iron powder with Me3AsI2 results in the formation of a trigonal bipyramidal complex, [FeI3(AsMe3)2], which features the iodide ligands in the equatorial

  摘要Me3AsI2与未活化的铁粉的反应为碘化铁（III）的配位化学提供了一个合成入口，由于母体卤化物FeI3的稳定性低，传统路线无法实现该配位化学。铁粉与Me3AsI2的反应导致形成三角双锥体络合物[FeI3（AsMe3）2]，其特征是在赤道位置具有碘化物配体，而Me3As基团占据轴向位置。该络合物是碘化铁（III）络合物的罕见实例，并且是单齿叔a配体的第一个铁（III）络合物。通过铁粉的直接氧化制备[FeI3（AsMe3）2]进一步证明，可以使用“硬”过渡金属中心（例如铁（III））制备“软”供体配体的配合物，直接违反了HSAB原则。[FeI3（AsMe3）2]的结构与所有先前报道的[MX3（EMe3）2]（M =主族或过渡金属，X =卤化物，E = N，P，As）三角双锥体结构同构。
• Facile one-step synthesis of the cobalt(III) and nickel(III) tertiary arsine complexes [MI3(AsMe3)2](M = Co or Ni) directly from the powdered elemental metals
  作者：Neil Bricklebank、Stephen M. Godfrey、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1039/dt9960000157

  日期：——

  Diiodotrimethylarsine, Me3AsI2, was treated with cobalt or nickel metal powder to give the metal(III) complex, [MI3(AsMe3)2]. In the case of cobalt, a metal(II) complex, [AsMe3I][CoI3(AsMe3)], was also produced, whereas for the nickel reaction only the nickel(III) complex, [NiI3(AsMe3)2], was formed in quantitative yield. The only other product from the reactions was diiodine, which was detected spectrophotometrically. Both complexes have been crystallographically characterised and found to be isostructural, consisting of a metal(III) atom with three equatorial iodide ligands capped by two trimethylarsine ligands. These complexes are unique examples of X-ray structural characterisation of compounds of this stoichiometry. Conventional wisdom would not have expected the ‘soft’ ligands I– and AsMe3 to bind to the relatively hard metal(III) centre.

  用钴或镍金属粉末处理二碘三甲基胂 Me3AsI2，可得到金属（III）络合物 [MI3(AsMe3)2]。在钴反应中，还生成了金属（II）络合物 [AsMe3I][CoI3(AsMe3)]，而在镍反应中，只生成了定量的镍（III）络合物 [NiI3(AsMe3)2]。反应中唯一的其他产物是二碘，它是通过分光光度法检测到的。对这两种配合物进行了晶体学表征，发现它们结构相同，都是由一个金属（III）原子与三个赤道碘配体和两个三甲基胂配体组成。这些复合物是对这种化学计量的化合物进行 X 射线结构表征的独特实例。传统观点认为，"软 "配体 I- 和 AsMe3 不会与相对较硬的金属（III）中心结合。
• Umland, Peter; Vahrenkamp, Heinrich, Chemische Berichte, 1982, vol. 115, # 11, p. 3565 - 3579
  作者：Umland, Peter、Vahrenkamp, Heinrich

  DOI：——

  日期：——
• The Oxidation of Gold Powder by Me3El2(E P, As) under Ambient Conditions; Structures of[AuI3(PMe3)2],[AuI3(AsMe3)], and[(Me3PO)2H][AuI2]
  作者：Stephen M. Godfrey、Nicholas Ho、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1002/anie.199623441

  日期：1996.11.1