Triphenylsilylaethinyllithium | 70975-24-5

• 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: Triphenylsilylaethinyllithium
• CAS: 70975-24-5
• 化学式: C₂₀H₁₅LiSi
• 分子量: 290.366
• InChiKey: MFJLSSSIGARZLH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.83
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  、 Triphenylsilylaethinyllithium 以 乙醚 为溶剂， 生成 (E)-bis(trimethyl-l5-phosphaneyl)((triphenylsilyl)ethynyl)(1,4,6-tris(trimethylsilyl)hexa-3-en-1,5-diyn-3-yl)nickel
  参考文献：
  名称：

  Nickel-mediated synthesis of dialkynyl and trialkynyl ethenes — demetallation reactions

  摘要：

  Metalorganic syntheses of the title compounds starting from l-alkynes and Ni(cod)(PMe3)(2) or Ni(PM3)(4) consist of less than six steps and afford better than 50% overall yields of isolated compounds. Elimination of the metal by reductive C,C coupling in diorganonickel complexes under 1 bar CO and workup in aqueous hydrochloric acid are the key steps in the preparation af(RC=C)R'C=C(R) (C=CR) (R=SiMe3, CMe3; R'=H, CH3, C6H5, C=CH, C=CCH3, C=CCMe3, C=CSiMe3, C=CSiPh3, C=CC6H5, C=CC6H4F, C=CC6H11, C=CCH2SiMe3). Starting from 3-bromopropyne the initial C,C-coupling reaction is followed by an oxidative addition of the CH,Br function to zerovalent nickel and a second C,C coupling, which generates the tetradecadienetetrayne skeleton of (RC=C)(R)C=(RC=C)C-C=C-CH2-CH2-C=C-(RC=C)C=C(C=CR)-(R) (R=SiMe3).

  DOI：

  10.1016/s0020-1693(97)05485-6

文献信息

• Synthesis and Characterization of Redox-Active C₄-Bridged Rigid-Rod Complexes with Acetylide-Substituted Manganese End Groups
  作者：Koushik Venkatesan、Thomas Fox、Helmut W. Schmalle、Heinz Berke

  DOI：10.1021/om049252p

  日期：2005.6.1

  The symmetric d(5) trans-bis(alkynyl) complexes [Mn(R'2PCH2CH2PR'(2))(2)(C CR)(2)] (R'= Me, R = SiEt3, 3a; R' = Me, R = (SiPr3)-Pr-i, 3b; R' = Me, R = Si(Bu-t)Me-2, 3c; R' = Et, R = SiEt3, 4a; R' = Et, R = (SiPr3)-Pr-i, 4b; R' = Et, R = Si(Bu-t)Me-2, 4c) can be prepared by the reaction of [Mn(R'2PCH2CH2PR'(2))(2)Br-2] (R' = Me, 1; R' = Et, 2) with 2 equiv of LiC CR (R = SiEt3, (SiPr3)-Pr-i, Si(Bu-t)Me-2). The reactions of species 3 and 4 with [Cp2Fe] [PF6] yield the corresponding d4 complexes [Mn(dmpe)(2)(C CR)(2)] [PF6] (R' = Me, R = SiEt3, 5a; R' = Me, R = (SiPr3)-Pr-i, 5b; R' = Me, R = Si(Bu-t)Me-2, 5c; R' = Et, R = SiEt3, 6a; R' = Et, R = (SiPr3)-Pr-i, 6b; R' = Et, R = Si(Bu-t)Me-2, 6c). The asymmetrically substituted trans-bis(alkynyl) complexes [Mn(dmpe)(2)(C CR)(C CH)] [PF6] (R' = Me, R = SiEt3, 10a; R' = Me, R = (SiPr3)-Pr-i, 10b; R' = Me, R = Si(Bu-t)Me-2, 10c) are prepared by the reaction of the vinylidene compounds Mn(dmpe)(2)(C CR)(C CH2) (R' = Me, R = SiEt3, 9a; R' = Me, R = (SiPr3)-Pr-i, 9b; R' = Me, R = Si(Bu-t)Me-2, 9c) with 2 equiv of [Cp2Fe] [PF6] and 1 equiv of quinuclidine. The mixed-valent complexes [Mn(dmpe)(2)(C CR)}(2)(mu-C-4)] [PF6] [11](+) are obtained by the reaction of 10 with 1 equiv of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The neutral dinuclear Mn(II)/Mn(II) compounds [Mn(dmpe)(2)(C CR)}(2)(mu-C-4)] (R = SiEt3, 11a; R = (SiPr3)-Pr-i, 11b; R = Si(Bu-t)Me-2, 11c) are synthesized by the reduction of [11](+) with Co(C5Me5)(2). Complexes [11](+) can also be oxidized with [Cp2-Fe] [PF6] to produce the dicationic Mn(III)/Mn(III) species [Mn(dmpe)(2)(C CR3)}(2)(mu-C-4)] [PF6](2) (R = SiEt3, [11a](2+); R = (SiPr3)-Pr-i, [11b](2+); R = Si(Bu-t)Me-2, [11c](2+)). Both redox processes are fully reversible. The dinuclear compounds have been characterized by NMR, IR, and Raman spectroscopy, cyclic voltammetry, and elemental analyses. X-ray diffraction studies have also been performed on several complexes.
• Nickel-mediated synthesis of dialkynyl and trialkynyl ethenes — demetallation reactions
  作者：Hans-Freidrich Klein、Andreas Peterman

  DOI：10.1016/s0020-1693(97)05485-6

  日期：1997.9

  Metalorganic syntheses of the title compounds starting from l-alkynes and Ni(cod)(PMe3)(2) or Ni(PM3)(4) consist of less than six steps and afford better than 50% overall yields of isolated compounds. Elimination of the metal by reductive C,C coupling in diorganonickel complexes under 1 bar CO and workup in aqueous hydrochloric acid are the key steps in the preparation af(RC=C)R'C=C(R) (C=CR) (R=SiMe3, CMe3; R'=H, CH3, C6H5, C=CH, C=CCH3, C=CCMe3, C=CSiMe3, C=CSiPh3, C=CC6H5, C=CC6H4F, C=CC6H11, C=CCH2SiMe3). Starting from 3-bromopropyne the initial C,C-coupling reaction is followed by an oxidative addition of the CH,Br function to zerovalent nickel and a second C,C coupling, which generates the tetradecadienetetrayne skeleton of (RC=C)(R)C=(RC=C)C-C=C-CH2-CH2-C=C-(RC=C)C=C(C=CR)-(R) (R=SiMe3).