Methylen-magnesium-iodid | 27329-48-2

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: Methylen-magnesium-iodid
• 英文别名: Methylenbis-magnesiumjodid；methanediyl-bis-magnesium iodide
• CAS: 27329-48-2
• 化学式: CH₂I₂Mg₂
• 分子量: 316.446
• InChiKey: QUAHOPFDMLVMBN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.47
• 重原子数：
  5.0
• 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

• 作为反应物：
  描述：

  η5-cyclopentadienyl(diphenylacetylene)bis(trimethyl phosphite)molybdenum tetrafluoroborate 、 Methylen-magnesium-iodid 以 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 以45%的产率得到bis(dimethoxyphosphanyloxy)-difluoroboranuide;cyclopenta-1,3-diene;molybdenum(2+);2-phenylethynylbenzene
  参考文献：
  名称：

  Reaction of the η²(4e)-donor alkyne complexes [Mo{η²(4e)-R¹C₂R²}{P(OMe)₃}₂(η-C₅H₅)](R¹= R²= Ph or Me; R¹= Me, R²= Ph) with the Grignard reagents MgR³(X)(R³= Me, Et, CH₂Ph, CH₂CHCH₂or CHCH₂) and CH₂(MgI)₂

  摘要：

  Reaction of the complex [Mo{eta(2)(4e)-PhC(2)Ph}{P(OMe)(3)}(2)(eta-C5H5)][BF4]1 with MgR(X) (R = Me, Et or PhCH(2)) afforded good yields of [Mo{eta(2)(4e)-PhC(2)Ph}R{P(OMe)(3)}(eta-C5H5)]. Unexpectedly, reaction of 1 with the 1,1-di-Grignard reagent CH2(MgI)(2) gave the X-ray crystallographically identified zwitterionic complex [Mo{eta(2)(4e)-PhC(2)Ph}{eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)], similar reactions with the but-2-yne and 1-phenylprop-2-yne complexes affording the analogous [Mo{eta(2)(4e)-RC(2)R(2)){eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)] (R = R(2) = Me; R = Me, R(2) = Ph). Treatment of the zwitterionic diphenylacetylene- and 1-phenylprop-2-yne-substituted complexes with K[BHBu(3)(s)] gave the anionic eta(2)(3e)-vinyl complexes K[Mo{=C(R)CH(Ph)}{eta(2)-P(OMe)(2)OBF2OP(OMe)(2)(eta-C5H5)] (R = Ph or Me). Protonation (HBF4 . Et(2)O) of the diphenyl-substituted eta(2)(3e)-vinyl complex followed by addition of carbon monoxide, trimethyl phosphite, or diphenylacetylene afforded trans-stilbene and the complexes [Mo(CO)(2){eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta(2)-C5H5)], [Mo{P(OMe)(3)}(2){eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)] and [Mo{eta(2)(4e)-PhC(2)Ph}{eta(2)P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)] respectively. When CH2=CHCH2MgBr was added to 1 an unstable compound was formed, which on addition of P(OMe)(3) gave [Mo{eta(3)-C(Ph)=C(Ph)CH2CH=CH2}{P(OMe)(3)}(2)(eta-C5H5)], the identity of which was confirmed by X-ray crystallography. This reaction is explained in terms of an unusual metalla-3,3-sigmatropic shift process. A similar reaction between 1 and CH2=CHMgBr followed by addition of P(OMe)(3) surprisingly gave the eta(3)-cyclopropenyl complex [Mo(eta(3)-C(3)Ph(2)Me){P(OMe)(3)}(2)(eta-C5H5)]. The complex [Mo{eta(2)(4e)-PhC(2)Ph}Me{P(OMe)(3)}(eta-C5H5)] reacted thermally (78 degrees C) with an excess of PhC(2)Ph to give the X-ray crystallographically identified complex [MoH(eta(4)-C(5)H(2)Ph(4)){P(OMe)(3)}(eta-C5H5)], which on heating (100 degrees C) afforded the dihydride [MoH2(eta(5)-C(5)HPh(4))(eta-C5H5)].

  DOI：

  10.1039/dt9960003387
• 作为产物：
  描述：

  二碘甲烷 在 amalgamated magnesium 作用下， 以 乙醚 为溶剂， 生成 Methylen-magnesium-iodid
  参考文献：
  名称：

  宝石双金属化合物。亚甲基卤化镁的“ Wittig”反应。一种从醛和酮获得亚甲基烯烃的简单方法

  摘要：

  DOI：

  10.1016/s0040-4039(01)89632-5