2,6-dibenzhydryl-N-(2,6-dibenzhydryl-4-methyl-N-trimethylsilylanilino)germylidynegermyl-4-methyl-N-trimethylsilylaniline | 1346135-53-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 2,6-dibenzhydryl-N-(2,6-dibenzhydryl-4-methyl-N-trimethylsilylanilino)germylidynegermyl-4-methyl-N-trimethylsilylaniline
• CAS: 1346135-53-2
• 化学式: C₇₂H₇₂Ge₂N₂Si₂
• 分子量: 1166.73
• InChiKey: HBDSMQIUPZJCJV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.16
• 重原子数：
  78
• 可旋转键数：
  18
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二硫化碳 、 2,6-dibenzhydryl-N-(2,6-dibenzhydryl-4-methyl-N-trimethylsilylanilino)germylidynegermyl-4-methyl-N-trimethylsilylaniline 以 not given 为溶剂， 生成
  参考文献：
  名称：

  用酰胺基-地germyne轻松地将二氧化碳还原为一氧化碳

  摘要：

  服用嘶嘶声出：与盖吖digermyne化合物葛单键已经显示出CO定量减少2在温度至CO低至-40℃。光谱和计算技术已经探究了这种前所未有的反应的机理，并且涉及到亚稳中间体（见图片； Ar * = C 6 H 2 {C（H）Ph 2 } 2 Me-2,6,4）。

  DOI：

  10.1002/anie.201203607
• 作为产物：
  描述：

  [(N(C₆H₂{C(H)Ph₂}₂Me-2,6,4)(SiMe₃))GeCl] 在 (Mg(CH(mesitylNCCH₃)2))2 作用下， 以 not given 为溶剂， 以55%的产率得到2,6-dibenzhydryl-N-(2,6-dibenzhydryl-4-methyl-N-trimethylsilylanilino)germylidynegermyl-4-methyl-N-trimethylsilylaniline
  参考文献：
  名称：

  A Digermyne with a Ge–Ge Single Bond That Activates Dihydrogen in the Solid State

  摘要：

  The reduction of the bulky amido-germanium-(II) chloride complex, LGeCl (L = N(SiMe3)(Ar*); Ar* = C6H2Me{C(H)Ph-2}(2)-4,2,6), with the magnesium(I) dimer, [{((Mes)Nacnac)Mg}(2)] ((Mes)Nacnac = [(MesNCMe)(2)CH](-); Mes = mesityl), afforded LGeGeL, which represents the first example of a digermyne with a Ge-Ge single bond. Computational studies of the compound have highlighted significant electronic differences between it and 'multiply bonded digermynes. LGeGeL was shown to cleanly activate H-2 in solution or the solid state, at temperatures as low as 10 degrees C, to give the mixed valence compound, LGeGe(H)(2)L.

  DOI：

  10.1021/ja209215a

文献信息

• Synthesis and characterization of extremely bulky amido-germanium(II) halide complexes
  作者：Terrance J. Hadlington、Jiaye Li、Cameron Jones

  DOI：10.1139/cjc-2013-0394

  日期：2014.6

  The extremely bulky aryl/silyl secondary amines, HN(Ar)(SiMe₃), Ar = C₆H₂-i-Pr₂(CPh₃)-2,6,4 (L^DipH), C₆H₂C(H)Ph₂}₂-i-Pr-2,6,4 (L^†H), or C₆H₂C(H)Ph₂}₂-t-Bu-2,6,4 (L^t-BuH), have been synthesized via salt metathesis reactions between the appropriate lithium anilide complex and ClSiMe₃. The related diaryl secondary amines, HN(Ar*)(R), Ar* = C₆H₂C(H)Ph₂}₂Me-2,6,4 and R = C₆H₃Me₂-3,5 (L^MeH), C₆H₃(CF₃)₂-3,5 (L^CF3H), or C₆H₂-i-Pr₃-2,4,6 (L^TripH), were prepared via palladium catalyzed cross-coupling reactions. Three of the amines were crystallographically characterized. Treatment of GeCl₂·dioxane with 1 equiv. of each of the deprotonated amines led to the isolation of the amido-germanium(II) chloride complexes, [LGeCl] (L = L^†, L^t-Bu, L^CF3, or L^Trip). Similarly, reaction of the known amido-digermyne, [L*Ge–GeL*] (L* = –N(Ar*)(SiMe₃)), with I₂ resulted in the oxidative cleavage of the Ge–Ge bond of the digermyne, and the formation of the first two-coordinate amido-germanium(II) iodide complex, [L*GeI]. Crystallographic characterization of [L^t-BuGeCl] and [L*GeI] revealed both to have similar monomeric structures. The compounds described in this study should prove useful as synthons for synthetic chemists working in the field of low oxidation state main group chemistry.

  极为庞大的芳基/硅基二级胺，HN(Ar)(SiMe3)，其中Ar = C6H2-i-Pr2(CPh3)-2,6,4 (LDipH)，C6H2C(H)Ph2}2-i-Pr-2,6,4 (L†H)，或C6H2C(H)Ph2}2-t-Bu-2,6,4 (Lt-BuH)，已通过适当的锂苯胺配合物与ClSiMe3之间的盐转化反应合成。相关的二芳基二级胺，HN(Ar*)(R)，其中Ar* = C6H2C(H)Ph2}2Me-2,6,4，R = C6H3Me2-3,5 (LMeH)，C6H3(CF3)2-3,5 (LCF3H)，或C6H2-i-Pr3-2,4,6 (LTripH)，通过钯催化的交叉偶联反应制备。其中三种胺已经进行了晶体学表征。将GeCl2·二氧六环与每种脱质子化胺的1当量处理，得到了翻译的氨基锗(II)氯化物配合物，[LGeCl] (L = L†, Lt-Bu, LCF3, 或LTrip)。类似地，已知的氨基二锗烷，[L*Ge-GeL*] (L* = -N(Ar*)(SiMe3))，与I2反应导致了二锗烷的氧化裂解，形成了第一个二配位的氨基锗(II)碘化物配合物，[L*GeI]。对[Lt-BuGeCl]和[L*GeI]的晶体学表征显示它们都具有类似的单体结构。本研究描述的化合物应该对在低氧化态主族化学领域工作的合成化学家具有实用价值。
• A Digermyne with a Ge–Ge Single Bond That Activates Dihydrogen in the Solid State
  作者：Jiaye Li、Christian Schenk、Catharina Goedecke、Gernot Frenking、Cameron Jones

  DOI：10.1021/ja209215a

  日期：2011.11.23

  The reduction of the bulky amido-germanium-(II) chloride complex, LGeCl (L = N(SiMe3)(Ar*); Ar* = C6H2MeC(H)Ph-2}(2)-4,2,6), with the magnesium(I) dimer, [((Mes)Nacnac)Mg}(2)] ((Mes)Nacnac = [(MesNCMe)(2)CH](-); Mes = mesityl), afforded LGeGeL, which represents the first example of a digermyne with a Ge-Ge single bond. Computational studies of the compound have highlighted significant electronic differences between it and 'multiply bonded digermynes. LGeGeL was shown to cleanly activate H-2 in solution or the solid state, at temperatures as low as 10 degrees C, to give the mixed valence compound, LGeGe(H)(2)L.
• The Facile Reduction of Carbon Dioxide to Carbon Monoxide with an Amido‐Digermyne
  作者：Jiaye Li、Markus Hermann、Gernot Frenking、Cameron Jones

  DOI：10.1002/anie.201203607

  日期：2012.8.20

  Taking the fizz out: A digermyne compound with a GeGe single bond has been shown to quantitatively reduce CO2 to CO at temperatures as low as −40 °C. The mechanism of this unprecedented reaction has been probed by spectroscopic and computational techniques and involves a metastable intermediate (see picture; Ar*=C6H2C(H)Ph2}2Me‐2,6,4).

  服用嘶嘶声出：与盖吖digermyne化合物葛单键已经显示出CO定量减少2在温度至CO低至-40℃。光谱和计算技术已经探究了这种前所未有的反应的机理，并且涉及到亚稳中间体（见图片； Ar * = C 6 H 2 C（H）Ph 2 } 2 Me-2,6,4）。