methoxydimethylgermane | 150468-09-0

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: methoxydimethylgermane
• 英文别名: dimethylmethoxygermane；Methoxy(dimethyl)germane
• CAS: 150468-09-0
• 化学式: C₃H₁₀GeO
• 分子量: 134.702
• InChiKey: MHUIFJOCQKXCCI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.62
• 重原子数：
  5
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  methoxydimethylgermane 以 甲醇 为溶剂， 生成 methoxydimethylgermane
  参考文献：
  名称：

  快速瞬态亚甲基在甲醇和四氢呋喃溶液中反应性的动力学研究

  摘要：

  激光闪光光解技术已被用于研究二甲基亚锗烯（GeMe 2），二苯锗烯（GePh 2）以及一系列环取代的二芳基锗烯（GeAr 2）在甲醇（MeOH）和四氢呋喃（THF）溶液中的反应性。亚二甲苯基作为与O-供体溶剂的相应路易斯酸碱配合物而存在。在THF溶液中，二聚化为相应的二锗烯是一种重要的衰变模式，特别是对于GeMe 2 -THF配合物，尽管对于二芳基体系而言，与己烷溶液相比，其降解速度显着降低。另一方面，在MeOH中检测不到二聚化，其中GeAr 2-MeOH配合物在低激光强度和20-50μs范围内的寿命下以伪一级动力学衰减。GeMe 2 -MeOH络合物的寿命约为 在类似条件下为4μs。溶剂的动力学同位素效应与溶剂催化的质子转移相一致，从而产生相应的烷氧基氢化锗烷，这是导致二甲苯-MeOH配合物衰变的过程。它们的衰变分别由强酸和强碱（例如甲磺酸和甲醇钠）加速，它们以大约0.2的速率常数淬灭GePh

  DOI：

  10.1021/om8010323

文献信息

• Organogermanium Reactive Intermediates. The Direct Detection and Characterization of Transient Germylenes and Digermenes in Solution
  作者：William J. Leigh、Cameron R. Harrington、Ignacio Vargas-Baca

  DOI：10.1021/ja046308y

  日期：2004.12.1

  Diphenylgermylene (Ph2Ge) and its Ge=Ge doubly bonded dimer, tetraphenyldigermene (6a), have been characterized directly in solution for the first time by laser flash photolysis methods. The germylene is formed via (formal) cheletropic photocycloreversion of 3,4-dimethyl-1,1-diphenylgermacyclopent-3-ene (4a), which is shown to proceed in high chemical (>95%) and quantum yield (phi = 0.62) by steady-state

  Diphenylgermylene (Ph2Ge) 及其 Ge=Ge 双键二聚体四苯基二锗烯 (6a) 首次通过激光闪光光解方法直接在溶液中表征。锗烯是通过 3,4-二甲基-1,1-二苯基锗环戊-3-烯 (4a) 的（正式）螯合光环回复形成的，这表明其以高化学（> 95%）和量子产率（phi = 0.62）进行) 通过使用甲醇、乙酸、异戊二烯和三乙基硅烷进行稳态捕获实验。4a 在 23 摄氏度干燥脱氧己烷中的闪光光解导致迅速形成分配给 Ph2Ge 的瞬态（λ（最大）= 500 nm；epsilon（最大）= 1650 M（-1）cm（-1）），它以二阶动力学衰减（tau 大约 3 微米），伴随着分配给二锗烯 6a（tau 大约 40 微米；λ（最大）= 440 nm）的第二个瞬态物种的生长。从 1,1-二甲基-和 1,1-二甲基-3,4-二甲基锗环戊-3-烯（分别为 4b 和 4c）获得了类似的结果，它们提供了
• Chemistry of heavy carbene analogues R2M (M  Si, Ge, Sn)
  作者：Beatrix Klein、Wilhelm P. Neumann、Markus P. Weisbeck、Stefan Wienken

  DOI：10.1016/0022-328x(93)80047-f

  日期：1993.3

  new) substituted organogermanium hydrides of the type X-Me2Ge-H, 3, 5–12. The more acidic compounds form the more stable hydrides. Only PhSMe2GeH, 11, brings about spontaneous hydrogermylation of certain alkenes. With suitable donors 1 reversible forms complexes Me2Ge · D, 15, which are, in the case of XH compounds, to be considered as precursors of the insertion products. These complexes are discussed

  游离的二甲基亚甲基Me 2 Ge，1平稳地插入水，氧化氘，醇，羧酸，肟和邻苯二甲酰亚胺的OH，SH或NH键中，生成（大部分为新的）取代的有机锗氢化物类型X-ME 2的Ge-H，3，5-12。酸性较高的化合物形成更稳定的氢化物。只有PhSMe 2 GeH，11会引起某些烯烃的自发加氢麦芽糖化反应。使用合适的供体1可逆形式的络合物Me 2 Ge·D，15在X = H化合物的情况下，被视为插入产物的前体。这些配合物被讨论为中间体，可以加成烯烃和（立体选择性地）加成炔烃。
• Synthesis, Structure, and Properties of Three- and Six-Membered Metallacycles Composed of Iron, Germanium, and Sulfur Atoms
  作者：Masaaki Okazaki、Hiromitsu Kimura、Takashi Komuro、Hiroshi Okada、Hiromi Tobita

  DOI：10.1246/cl.2007.990

  日期：2007.8.5

  Ultraviolet irradiation of Cp∗(CO)2FeGeMe2SPh in the presence of acetone afforded trans-[Cp∗Fe(CO)μ-κ2Ge,S-GeMe2SPh}]2, while the introduction of a bulkier substituent on the sulfur atom allowed s...

  在丙酮存在下，Cp∗(CO)2FeGeMe2SPh 的紫外线照射得到反式-[Cp∗Fe(CO)μ-κ2Ge,S-GeMe2SPh}]2，而在硫原子上引入更大的取代基则允许 s。 ..
• A radiochemical study of isomerization of dimethylgermylium ion, with the reaction of Me2HGe+ cation with methyl tert-butyl ether as example
  作者：D. L. Myalochkin、T. A. Kochina、D. V. Vrazhnov、V. V. Avrorin、E. N. Sinotova

  DOI：10.1134/s1066362210010224

  日期：2010.2

  The reaction of dimethylgermylium ion with methyl tert-butyl ether in the gas phase was studied by the radiochemical method, and the mechanisms of the corresponding ion-molecule reactions were suggested. The possibility of the existence of germylium ions generated by the nuclear-chemical method was proved by the example of dimethylgermylium ion. Possible pathways of transformation of (CH3)(2)HGe+ cation into other isomeric forms were analyzed by B3LYP calculations with 6-31G* and aug-cc-pVDZ basis sets.
• Time-Resolved Spectroscopic Studies of the Reactivities of Dimethylgermylene and Tetramethyldigermene in Solution
  作者：William J. Leigh、Farahnaz Lollmahomed、Cameron R. Harrington

  DOI：10.1021/om0600083

  日期：2006.4.1

  Dimethylgermylene (GeMe2) has been generated and studied by laser flash photolysis of 1,1-dimethyl-and 1,1,4-trimethyl-3-phenylgermacyclopent-3-ene (3a and 3b, respectively) in hexane solution, where it exhibits lambda(max) = 470 nm and decays on the microsecond time scale with second-order kinetics. In the absence of scavengers the decay of GeMe2 is accompanied by the growth of absorptions due to tetramethyldigermene (Ge2Me4; lambda(max) = 370 nm), which decays over the next ca. 100 mu s. Absolute rate constants for reaction of GeMe2 with several reagents have been determined, including acetic acid, CCl4, oxygen, n-butyl- and triethylamine, a terminal alkene and alkyne, two dienes, and the group 14 trialkymetallyl hydrides R3MH (M = Si, Ge, Sn; R = Et or n-Bu). The rate constants agree closely with gas-phase values for the same or similar substrates. The data are compared to those for reaction of GePh2 with the same set of reagents, showing GeMe2 to be significantly more reactive than its phenylated analogue in every case. Evidence of reversibility is obtained for the reactions with the alkene and dienes, which are thought to yield the corresponding three-membered germanocycles as primary products; the equilibrium constants for these reactions are also considerably higher than those for reaction of GePh2. Comparisons are also made with published data for SiMe2 in solution. Absolute rate constants for reaction of Ge2Me4 have also been measured or assigned upper limits and are compared to those for the tetraphenyl analogue (Ge2Ph4), providing the first quantitative assessment of the effects of substituents on the reactivity of the Ge=Ge bond.