cis,mer-[WCl2(NNCH=CHCH=CH)(PMe2Ph)3] | 172099-74-0

• 英文名称: cis,mer-[WCl2(NNCH=CHCH=CH)(PMe2Ph)3]
• CAS: 172099-74-0
• 化学式: C₂₈H₃₇Cl₂N₂P₃W
• 分子量: 749.292
• InChiKey: HRUULMHIJNOAPR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  cis,mer-[WCl2(NNCH=CHCH=CH)(PMe2Ph)3] 、 一氧化碳 以 甲苯 为溶剂， 生成 cis,trans-[WCl2(NNCH=CHCH=CH)(CO)(PMe2Ph)2]
  参考文献：
  名称：

  由钨二氮配合物衍生的钨吡咯亚胺配合物的选择性 N-N 和 W-N 键断裂

  摘要：

  [WX2(NNCH=CHCH=CH)(L)(PMe2Ph)2] ) (X = Cl, Br, I; L = PMe2Ph (6), CNBut, CO, PhC≡ CH、PhCHO、Br) 与 LiAlH4 或 KOH 产生吡咯、1-氨基吡咯和氨，其中反应条件和配体 L 的性质对吡咯/1-氨基吡咯的选择性有显着影响。因此，用LiAlH4还原顺，反-([WBr2(NNCH=CHCH=CH)(CNBut)(PMe2Ph)2])，然后进行甲醇分解，以几乎定量的产率得到吡咯和氨。另一方面，当 L = CO、PhC≡CH 或 PhCHO 时，通过 KOH 在醇中的反应从配合物中定量产生 1-氨基吡咯。虽然在乙醇中用 KOH 对 6 进行类似处理，在 N2 气氛下以低选择性得到吡咯和 1-氨基吡咯，1-氨基吡咯在 1 个大气压的 CO 下以极好的收率由 6 生产。相反，吡咯和氨是由 6b (X = Br)

  DOI：

  10.1246/bcsj.72.425
• 作为产物：
  描述：

  2,5-二甲氧基四氢呋喃 、 盐酸 、 cis,mer-[WCl2(NNH2)(PMe2Ph)3] 以 四氢呋喃 为溶剂， 以44%的产率得到cis,mer-[WCl2(NNCH=CHCH=CH)(PMe2Ph)3]
  参考文献：
  名称：

  Synthesis and Reactivities of Pyrrolylimido Complexes of Molybdenum and Tungsten: Formation of Pyrrole and N-Aminopyrrole from Molecular Nitrogen

  摘要：

  Hydrazido(2-) complexes trans-[MX(NNH2)(dppe)(2)](+) (M = Mo, W; X = F, Cl; dppe = Ph(2)PCH(2)CH(2)PPh(2)) and cis,mer-[WX(2)(NNH2)(PMe(2)Ph)(3)] (X = Cl, Br), which are readily derived from trans-[M(N-2)(2)(dppe)(2)] (1) and cis-[W(N-2)(2)(PMe(2)Ph)(4)] by protonation, condensed with 2,5-dimethoxytetrahydrofuran to afford pyrrolylimido complexes of the type trans-[MX(NNCH=CHCH=CH)(dppe)(2)](+) (3(+)) and cis,mer-[WX(2)(NNCH=CHCH=CH)(PMe(2)Ph)(3)] (6), respectively. Their structures were characterized spectroscopically and further confirmed by X-ray diffraction study. Electrophilic substitution reactions at the pyrrole ring in complexes 3(+) occurred selectively at the beta-position to give the corresponding beta-substituted pyrrolylimido complexes trans- [MX(NNCH=C(E)CH=CH)(dppe)(2)](+) (E Br, CN, SO3-, COR), although only chlorination of 3(+) with N-chlorosuccinimide in THF took place predominantly at the a-position. This beta-regioselectivity is in sharp contrast to the a-regioselectivity of free pyrrole and is probably caused by the steric effect of the dppe ligands. Complexes 3(+) were readily reduced under ambient conditions with LiAlH4 to liberate pyrrole and N-aminopyrrole in high yields. Further, the tetrahydrido complexes [MH(4)(dppe)(2)], which can be converted back into the original dinitrogen complexes 1, were recovered in moderate yields after the reduction. This accomplishes the synthetic cycle for pyrrole and N-aminopyrrole starting from the dinitrogen complexes 1. beta-Heptylpyrrole was also prepared by starting from 3c(+) (M = W, X = Cl) by the beta-selective heptanoylation followed by the reduction with LiAlH4. On the other hand, reduction of 6b (X = Br) with LiAlH4 predominantly produced pyrrole, whereas treatment of 6b with KOH/EtOH liberated N-aminopyrrole in a high yield.

  DOI：

  10.1021/ja00154a019

文献信息

• Preparation of Sulfide-Bridged Di- or Trinuclear Pyrrolylimido and Diazoalkane Complexes Derived from a Tungsten Dinitrogen Complex
  作者：Hidetake Seino、Yasushi Mizobe、Masanobu Hidai

  DOI：10.1246/bcsj.73.631

  日期：2000.3

  Tungsten pyrrolylimido and diazoalkane complexes, cis,mer-[WCl2(NNC4H4)(PMe2Ph)3] and cis,mer-[WCl2(NN=CRR′)(PMe2Ph)3], which are readily derived from the dinitrogen complex cis-[W(N2)2(PMe2Ph)4], reacted with [PPh4]2[WS4] to give the sulfide-bridged di- or trinuclear pyrrolylimido and diazoalkane complexes, [PPh4][WCl(NNC4H4)(PMe2Ph)2(μ-S)2WS2] (4) and [PPh4][WCl(NN=CRR′)(PMe2Ph)2(μ-S)2WS2] (R = R′

  钨吡咯亚胺和重氮烷配合物，cis,mer-[WCl2(NNC4H4)(PMe2Ph)3] 和 cis,mer-[WCl2(NN=CRR')(PMe2Ph)3]，它们很容易从二氮配合物 cis-[ W(N2)2(PMe2Ph)4]，与 [PPh4]2[WS4] 反应得到硫化物桥连的双核或三核吡咯亚胺和重氮烷配合物，[PPh4][WCl(NNC4H4)(PMe2Ph)2(μ- S)2WS2] (4) 和 [PPh4][WCl(NN=CRR')(PMe2Ph)2(μ-S)2WS2] (R = R' = Me (5a); R = Me, R' = Ph; R = H, R' = p-MeC6H4) 或 [WCl(NNC4H4)(PMe2Ph)2(μ-S)2}2W] (7) 和 [WCl(NN=CMePh)(PMe2Ph)2(μ -S)2}2W]。用四烷基秋兰姆二硫化物处理 4 或 5a 导致形