tert-butylgermane | 149540-54-5

• 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: tert-butylgermane
• 英文别名: tBuGeH3
• CAS: 149540-54-5
• 化学式: C₄H₁₂Ge
• 分子量: 132.729
• InChiKey: ZYTLADNCBYKKJS-UHFFFAOYSA-N

物化性质

• 沸点：
  50°C
• 密度：
  0,97 g/cm3
• 闪点：
  <23°C

计算性质

• 辛醇/水分配系数(LogP)：
  0.57
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• TSCA：
  No
• 安全说明：
  S15,S16,S33
• 危险类别码：
  R11
• 危险品运输编号：
  UN 1993

反应信息

• 作为反应物：
  描述：

  tert-butylgermane 在 [(PhB(CH₂PPh₂)₃)₃]RuH[η³-H₂SiMePh] 作用下， 以 氘代苯 为溶剂， 反应 24.0h， 以85%的产率得到
  参考文献：
  名称：

  Interconversion of η³-H₂SiRR′ σ-Complexes and 16-Electron Silylene Complexes via Reversible H–H or C–H Elimination

  摘要：

  Solid samples of eta(3)-silane complexes [PhBP3Ph](-) RuH(eta(3)-H2SiRR') (R,R' = Et-2, 1a; PhMe, 1b; Pb-2, 1c, MeMes, 1d) decompose when exposed to dynamic vacuum. Gas-phase H-2/D-2 exchange between isolated, solid samples of 1c-d(3) and 1c indicate that a reversible elimination of H-2 is the first step in the irreversible decomposition. An efficient solution-phase trap for hydrogen, the 16-electron ruthenium benzyl complex [PhBPPb3]Ru[eta(3)-CH2(3,5-Me2C6H3)] (3) reacts quantitatively with H2 in benzene via elimination of mesitylene to form the eta(5)-cyclohexadienyl complex [PhBP3Ph]Ru(eta(5)-C6H7) (4). This H2 trapping reaction was utilized to drive forward and quantify the elimination of H-2 from 1b,d in solution, which resulted in the decomposition of 1b,d to form 4 and several organosilicon products that could not be identified. Reaction of {[PhBP3Ph]Ru(mu-Cl)}(2) (2) with (THF)(2)Li(SiHMes(2)) forms a new eta(3)-H2Si species [PhBP3Ph]Ru[CH2(2-(eta(3)-H(2)SiMes)-3,5-Me2C6H2)] (5) which reacts with H-2 to form the eta(3)-H(2)SiMes(2) complex [PhBP3Ph]RuH(eta(3)-H(2)SiMes(2)) (1e). Complex 1e was identified by NMR spectroscopy prior to its decomposition by elimination of Mes(2)SiH(2) to form 4. DFT calculations indicate that an isomer of 5, the 16-electron silylene complex [PhBP3Ph]Ru(mu-H)(= SiMes(2)), is only 2 kcal/mol higher in energy than 5. Treatment of 5 with XylNC (Xyl = 2,6-dimethylphenyl) resulted in trapping of [PhBP3Ph]Ru(mu-H)(=SiMes(2)) to form the 18-electron silylene complex [PhBP3Ph]Ru(CNXyl)(mu-H)(=SiMes(2)) (6). A closely related germylene complex [PhBP3Ph]Ru[CN(2,6-diphenyl-4-MeC6H2)](H)(=(GeHBu)-Bu-t) (8) was prepared from reaction of (BuGeH3)-Bu-t with the benzyl complex [PhBP3Ph]Ru[CN(2,6-diphenyl-4-MeC6H2)][eta(1)-CH2(3,5-Me2C6H3)] (7). Single crystal XRD analysis indicated that unlike for 6, the hydride ligand in 8 is a terminal hydride that does not engage in 3c-2e Ru-H -> Ge bonding. Complex 1b is an effective precatalyst for the catalytic Ge-H dehydrocoupling of (BuGeH3)-Bu-t to form ((BuGeH2)-Bu-t)(2) (85% yield) and H-2.

  DOI：

  10.1021/ja501803w
• 作为产物：
  描述：

  叔丁基氯化镁 、 tetraethoxygermanium 在 LiAlH₄ 作用下， 以 二丁醚 为溶剂， 生成 tert-butylgermane
  参考文献：
  名称：

  以叔丁基锗烷为配体前体的锗烯桥连二铁配合物的合成及性能

  摘要：

  在新的烷基锗烷 tBuGeH3 存在下，CpFe(CO)2SiMe3 (Cp = η-C5H5) 的光解得到单（μ-锗烯）二铁络合物 Cp2Fe2(CO)3(μ-GeHtBu) (4) 和双 (μ -锗烯)二铁配合物 Cp2Fe2(CO)2(μ-GeHtBu)2 (5)。4的结构由X射线晶体学确定。

  DOI：

  10.1246/cl.1994.293

文献信息

• Integrated Palladium-Catalyzed Arylation of Heavier Group 14 Hydrides
  作者：Aldes Lesbani、Hitoshi Kondo、Yusuke Yabusaki、Misaki Nakai、Yoshinori Yamanoi、Hiroshi Nishihara

  DOI：10.1002/chem.201001437

  日期：2010.12.3

  A convenient procedure has been developed for the preparation of Group 14 compounds by integrated palladium‐catalyzed cross‐coupling of aromatic iodides with the corresponding Group 14 hydrides in the presence of a base. The reaction conditions can be applied to the cross‐coupling of tertiary, secondary, and primary Group 14 compounds. In most cases, the desired arylated products were obtained in synthetically

  在碱的存在下，通过钯催化的芳族碘化物与相应的14族氢化物的交叉偶联，已经开发出了一种方便的制备14族化合物的方法。该反应条件可用于第14组叔，仲和伯化合物的交叉偶联。在大多数情况下，所需的芳基化产物以合成有用的产率获得。即使在含OH，NH芳基碘的情况下2，CN或CO 2 R基团，具有良好的取得高产量的这些反应性官能团的耐受性进行的反应。这种方法的一个可能的应用是一个杀真菌二芳基（1的唯一合成ħ -1,2,4-三唑-1-基甲基）硅烷衍生物。
• Germyl- and Germylene-Bridged Complexes of Rh/Ir and Subsequent Chemistry of a Bridging Germylene Group
  作者：Md Hosnay Mobarok、Robert McDonald、Michael J. Ferguson、Martin Cowie

  DOI：10.1021/ic2021269

  日期：2012.4.2

  equiv of diphenylgermane at ambient temperature results in a novel mixed bis(μ-germylene) complex, [RhIr(CO)2(μ-GeHPh)(μ-GePh2)(dppm)2] (8), containing both mono- and disubstituted germylene fragments. Reaction of 1 equiv of diphenylgermane with complex 1 produces a similar monogermylene-bridged product, [RhIr(H)2(CO)2(μ-GePh2)(dppm)2] (9), while reaction of 1 with 2 equiv of diphenylgermane yields the

  合成了一系列中性和阳离子型亚甲基桥接的配合物和一个中性甲基（亚甲基）配合物，并通过NMR光谱和X射线晶体学进行了表征。1当量的锗烷RGeH 3（R = Ph，t Bu）与[RhIr（CO）3（dppm）2 ]（1）在低温下反应[RhIr（GeH 2 R）（H）（ CO）3（dppm）2 ]（R = Ph（3）或t Bu（4）），单Ge–H键活化的产物，经加热后转化为以germ烯桥连的二氢化物[RhIr（H）2（CO）2（μ-GeHR）（dppm）2 ]（R = Ph（5）或t Bu（6））通过激活第二个Ge–H键并伴有CO损失来激活。这两类化合物都具有以“摇篮形”几何形状折回的二膦。虽然化合物5分发生反应用额外phenylgermane在-40℃以得到锗烯-桥/甲锗烷基产物，[RhIr烷（GeH 2 PH）（H）2（CO）2（κ 1 -dppm）（μ-GeHPh）（μ -H）（dppm）]
• Zirconium-Catalyzed Heterodehydrocoupling of Primary Phosphines with Silanes and Germanes
  作者：Andrew J. Roering、Samantha N. MacMillan、Joseph M. Tanski、Rory Waterman

  DOI：10.1021/ic7013144

  日期：2007.8.1

  Triamidoamine-supported zirconium complexes catalyze the heterodehydrocoupling of primary phosphines with silane and germanes. In this catalysis, P-Si or P-Ge products are observed exclusively with no competitive P-P bond formation. Phosphido complexes (N3N)ZrPHR (N3N = N(CH2CH2NSiMe3)33-, R = Ph, 2; Cy, 3) were observed to be the catalyst resting state, and complex 2 was structurally characterized

  三酰氨基胺负载的锆络合物催化伯膦与硅烷和锗烷的杂脱氢偶联。在这种催化中，仅观察到P-Si或P-Ge产物，没有竞争性的PP键形成。观察到磷酸盐配合物（N 3 N）ZrPHR（N 3 N ＝ N（CH 2 CH 2 NS 1 Me 3）33-，R ＝ Ph，2； Cy，3）为催化剂静止状态，并且对配合物2进行了结构表征。
• [EN] COMPOSITIONS AND METHODS USING SAME FOR GERMANIUM SEED LAYER<br/>[FR] COMPOSITIONS ET LEURS PROCÉDÉS D'UTLISATION POUR COUCHE GERME DE GERMANIUM
  申请人：VERSUM MAT US LLC

  公开号：WO2022020705A1

  公开（公告）日：2022-01-27

  Precursors and methods for (a) forming silicon-containing films and (b) functionalizing substrate surfaces in order to generate a germanium seed layer suitable for deposition of Ge films. In one aspect, there is provided a precursor of Formula I and/or a precursor of Formula II, as described herein.

  提供一种(a)形成含硅膜层和(b)功能化衬底表面的前体方法，以生成适合沉积Ge膜的锗种子层。在一个方面，提供了一种公式I和/或公式II的前体，如本文所述。
• Rhodium‐Mediated Dehydrogenation of Hydroboranes and Group 14 Compounds: Base‐Stabilized Silylene and Germylene Complexes vs. Transmetalation
  作者：Shou‐Jen Hsiang、Paul G. Hayes

  DOI：10.1002/chem.202302925

  日期：2024.1.22

  Monocarbonyl rhodium complex LRh(CO), 1, which is stabilized by a pyrrole‐based bis(phosphinimine) pincer ligand (L=κ³‐NNN’=2,5‐[ⁱPr₂P=N(4‐ⁱPrC₆H₄)]₂‐N’(C₄H₂)⁻), serves as a versatile platform for the dehydrogenation of group 14 substrates. Reaction with primary and secondary silanes and germanes (MesSiH₃, Et₂SiH₂, Ph₂GeH₂, ^tBuGeH₃; Mes=mesityl) liberates H₂ and yields base‐stabilized tetrylene compounds of the form κ²‐L(CO)Rh(ER₂) (E=Si: R=Mes, H, 2; R=Et, 5; E=Ge: R=Ph, 6; R=^tBu, H, 8). The “:ER₂” fragment in these species bridges between the rhodium center and a phosphinimine donor. Preliminary reactions between pinacol (Pin) and κ²‐L(CO)Rh(ER₂), E=Si, Ge, indicate that such complexes can serve as silylene and germylene synthons, releasing :ER₂ and catalytically generating PinER₂. In contrast, combination of complex 1 and MesGeH₃ does not yield the anticipated dehydrogenation product, but rather, transmetalation similar to that observed upon reaction between 1 and 3,5‐dimethylphenylborane prevails.

  摘要单羰基铑络合物 LRh(CO) 1 由基于吡咯的双（膦酰亚胺）钳配体（L=κ3-NNN'=2,5-[iPr2P=N(4-iPrC6H4)]2-N'(C4H2)-）稳定，是第 14 组底物脱氢的多功能平台。与伯硅烷、仲硅烷和锗（MesSiH3、Et2SiH2、Ph2GeH2、tBuGeH3；Mes=甲硅烷基）反应释放出 H2，并生成形式为 κ2-L(CO)Rh(ER2)的碱稳定四甲苯化合物（E=Si：R=Mes，H，2；R=Et，5；E=Ge：R=Ph，6；R=tBu，H，8）。这些物质中的":ER2 "片段在铑中心和膦酰亚胺供体之间架桥。嚬哪醇（Pin）与κ2-L(CO)Rh(ER2)（E=Si、Ge）的初步反应表明，这些复合物可以作为硅烯和亚甲二氧基烯的合成物，释放出 :ER2 并催化生成 PinER2。相反，复合物 1 与 MesGeH3 的结合并没有产生预期的脱氢产物，而是出现了类似于 1 与 3,5-二甲基苯基硼烷反应时观察到的跨金属化现象。