Bis(pyrrolo[2,3-b]pyridin-1-yl)methyl-trimethylsilane | 1147859-84-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯并吡啶类
• 英文名称: Bis(pyrrolo[2,3-b]pyridin-1-yl)methyl-trimethylsilane
• 英文别名: bis(pyrrolo[2,3-b]pyridin-1-yl)methyl-trimethylsilane
• CAS: 1147859-84-4
• 化学式: C₁₈H₂₀N₄Si
• 分子量: 320.469
• InChiKey: WDVASYAWSTXHBR-UHFFFAOYSA-N

物化性质

• 沸点：
  480.1±45.0 °C(predicted)
• 密度：
  1.16±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.31
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  35.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Bis(pyrrolo[2,3-b]pyridin-1-yl)methyl-trimethylsilane 以 四氢呋喃 、 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  Reactivity of SiMe₃- and SnR₃-Functionalized Bis(7-azaindol-1-yl)methane with [PtR₂(μ-SMe₂)]_n (R = Me, Ph) and the Resulting Pt(II) and Pt(IV) Complexes

  摘要：

  Three new bis(7-azaindol-1-yl)methane (BAM) derivative ligands Me3Si-BAM (1a), Me3Sn-BAM (1b), and Ph3Sn-BAM (1c) have been synthesized, and their reactivities with [PtR2(mu-SMe2)](n), (R = Me, Ph) have been examined. Two Pt(II) complexes Pt(Me3Si-BAM)R-2 (R = Me, 2; Ph, 3) were obtained from the reactions of 1a. The reactions of 1b with [PtR2(mu-SMe2)](n) (R = Me, Ph) produced unexpected novel N,C,N-BAM Pt(IV) complexes Pt(N,C,N-BAM)(SnMe3)R-2 (R = Me, 4; Ph, 6) likely via oxidative cleavage of the C-BAM-Sn bond in 1b. 1c reacted with [PtPh2(mu-SMe2)](n) (n = 2, 3) yielding the anticipated Pt(II) complex Pt(Ph3Sn-BAM)Ph-2 (7), whereas its reaction with [PtMe2(mu-SMe2)](2) resulted in unusual Pt-II-Me and Sn-IV-Ph metathesis, yielding also 7 as one of the products. Mechanistic investigation was carried out to understand this phenomenon. The reactivities of 2 with MeI, MeOTf, and I-2 were examined. Its reaction with I-2 gave rise to Pt(Me3Si-BAM)I-2 (9) along with CH3I, indicating the possibility of functionalizing Pt-II-Me via iodinolysis. The reaction of Pt(NC,N-BAM)(SnMe3)Me-2 (4) with I-2 produced a number of unusual N,C,N-BAM Pt(IV) complexes including Pt(N,C,N-BAM)Me(I)(SnI2Me) (13) and Pt(N,C,N-BAM)Me(I)(I-3) (14) due to the electrophilic cleavage of the Sn-Me, Pt-Me and/or Pt-Sn bond(s) by I-2. For comparison, we also investigated the reaction of Pt(N,C,N-BAM)Me-3 (M1) with I-2 which was found to exhibit a high regioselectivity for the axial Pt-Me group, resulting in Pt(N,C,N-BAM)Me-2(I-3) (15) with the two Pt-Me being cis to each other. The reactions of 4 and M1 with I-2 are rare examples of Pt-IV-CH3 bond cleavage by the elimination of CH3I. The structures of 1a and complexes 2, 7, 9, and 13-15 were determined by X-ray diffraction analyses.

  DOI：

  10.1021/om900022n

文献信息

• Reactivity of SiMe₃- and SnR₃-Functionalized Bis(7-azaindol-1-yl)methane with [PtR₂(μ-SMe₂)]_<i>n</i> (R = Me, Ph) and the Resulting Pt(II) and Pt(IV) Complexes
  作者：Shu-Bin Zhao、Rui-Yao Wang、Suning Wang

  DOI：10.1021/om900022n

  日期：2009.4.27

  Three new bis(7-azaindol-1-yl)methane (BAM) derivative ligands Me3Si-BAM (1a), Me3Sn-BAM (1b), and Ph3Sn-BAM (1c) have been synthesized, and their reactivities with [PtR2(mu-SMe2)](n), (R = Me, Ph) have been examined. Two Pt(II) complexes Pt(Me3Si-BAM)R-2 (R = Me, 2; Ph, 3) were obtained from the reactions of 1a. The reactions of 1b with [PtR2(mu-SMe2)](n) (R = Me, Ph) produced unexpected novel N,C,N-BAM Pt(IV) complexes Pt(N,C,N-BAM)(SnMe3)R-2 (R = Me, 4; Ph, 6) likely via oxidative cleavage of the C-BAM-Sn bond in 1b. 1c reacted with [PtPh2(mu-SMe2)](n) (n = 2, 3) yielding the anticipated Pt(II) complex Pt(Ph3Sn-BAM)Ph-2 (7), whereas its reaction with [PtMe2(mu-SMe2)](2) resulted in unusual Pt-II-Me and Sn-IV-Ph metathesis, yielding also 7 as one of the products. Mechanistic investigation was carried out to understand this phenomenon. The reactivities of 2 with MeI, MeOTf, and I-2 were examined. Its reaction with I-2 gave rise to Pt(Me3Si-BAM)I-2 (9) along with CH3I, indicating the possibility of functionalizing Pt-II-Me via iodinolysis. The reaction of Pt(NC,N-BAM)(SnMe3)Me-2 (4) with I-2 produced a number of unusual N,C,N-BAM Pt(IV) complexes including Pt(N,C,N-BAM)Me(I)(SnI2Me) (13) and Pt(N,C,N-BAM)Me(I)(I-3) (14) due to the electrophilic cleavage of the Sn-Me, Pt-Me and/or Pt-Sn bond(s) by I-2. For comparison, we also investigated the reaction of Pt(N,C,N-BAM)Me-3 (M1) with I-2 which was found to exhibit a high regioselectivity for the axial Pt-Me group, resulting in Pt(N,C,N-BAM)Me-2(I-3) (15) with the two Pt-Me being cis to each other. The reactions of 4 and M1 with I-2 are rare examples of Pt-IV-CH3 bond cleavage by the elimination of CH3I. The structures of 1a and complexes 2, 7, 9, and 13-15 were determined by X-ray diffraction analyses.