bis(methyl-d3)magnesium | 64032-50-4

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 英文名称: bis(methyl-d3)magnesium
• CAS: 64032-50-4
• 化学式: C₂H₆Mg
• 分子量: 60.327
• InChiKey: KZLUHGRPVSRSHI-CKFJQVKPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.79
• 重原子数：
  3.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine cobalt(II) dichloride 、 bis(methyl-d3)magnesium 以 乙醚 为溶剂， 生成 [Co(C(2)H3)(2,6-(MeCN(2,6-(CHMe2)2C6H3))2C5H3N)]
  参考文献：
  名称：

  Investigations into the Mechanism of Activation and Initiation of Ethylene Polymerization by Bis(imino)pyridine Cobalt Catalysts:  Synthesis, Structures, and Deuterium Labeling Studies

  摘要：

  The activation of bis(imino)pyridine cobalt(II) precatalysts by MAO leads initially to a bis(imino)pyridine cobalt(I) cationic species with no cobalt-C(alkyl) bond into which insertion can occur. Mechanistic studies have shown that the initiation of polymerization from this species involves incorporation of alkyl groups from the cocatalyst, most likely involving attack of methide anion (from the counteranion) on a cobalt-ethylene species.

  DOI：

  10.1021/om049032b

文献信息

• Oxidatively induced M–C bond cleavage reactions of Cp*Ir(Me2SO)Me2 and Cp*Rh(Me2SO)Me2 (Cp* = η5-C5Me5)
  作者：Erik Fooladi、Todd Graham、Michael L. Turner、Bjørn Dalhus、Peter M. Maitlis、Mats Tilset

  DOI：10.1039/b107451m

  日期：——

  Electrochemical and chemical oxidation of Cp*Ir(Me2SO)Me2 (1; Cp* = η5-C5Me5) in Me2SO lead to the formation of methane and traces of ethene (ratio ca. 20 ∶ 1) as well as Cp*Ir(Me2SO)2Me+. Labeling studies indicate that three of the methane hydrogen atoms arise from the iridium-bonded methyl, while the fourth appears to arise from adventitious water. By contrast, oxidation of the rhodium analog Cp*Rh(Me2SO)Me2 gave only ethane and Cp*Rh(Me2SO)2Me+. Quantitative derivative cyclic voltammetry (DCV) showed that the disappearance of electrode-generated 1˙+ follows a rate law that is second order with respect to Ir. The Rh analog 6˙+ reacted at rates too great to be measured by DCV under these conditions. Possible mechanisms for these reactions are discussed, and particular attention is paid to the reactivity differences between Rh and Ir. Convenient new syntheses of Cp*Ir(Me2SO)Me2 and Cp*Rh(Me2SO)Me2, as well as X-ray structure determinations of these compounds and of Cp*Ir(Me2SO)2Me+, are reported.

  Cp*Ir(Me2SO)Me2（1；Cp* = δ-5-C5Me5）在 Me2SO 中发生电化学和化学氧化，生成甲烷和微量乙烯（比例约为 20∥1）以及 Cp*Ir(Me2SO)2Me+。标记研究表明，甲烷中的三个氢原子来自铱键甲基，而第四个氢原子似乎来自外来水。相比之下，氧化铑类似物 Cp*Rh(Me2SO)Me2 只得到乙烷和 Cp*Rh(Me2SO)2Me+。定量导数循环伏安法（DCV）显示，电极生成的 1Ë+ 的消失遵循与 Ir 有关的二阶速率定律。在这些条件下，Rh 类似物 6Ë+ 的反应速率太大，无法用 DCV 测定。讨论了这些反应的可能机制，并特别关注了 Rh 和 Ir 之间的反应性差异。报告了 Cp*Ir(Me2SO)Me2 和 Cp*Rh(Me2SO)Me2 的简便新合成方法，以及这些化合物和 Cp*Ir(Me2SO)2Me+ 的 X 射线结构测定。
• Coenzyme F430 from Methanogenic Bacteria: Detection of a Paramagnetic Methylnickel(II) Derivative of the Pentamethyl Ester by2H-NMR Spectroscopy
  作者：Shu-Kun Lin、Bernhard Jaun

  DOI：10.1002/hlca.19910740814

  日期：1991.12.11

  (F430M) of coenzyme F430 was prepared by in situ methylation with (CD3)2Mg and characterized by its isotropically shifted 2H-NMR spectrum. At −40°, the very broad D-signal of the axially coordinated CD3 group is found at −490 ppm. Comparison with the 2H- and 1H-NMR spectra of mcthyl(tetramethylcyclam)nickel(II) derivatives 4 ([NiII(CH3))(tmc)]CF3SO3 (4a) is the only isolated CH3–Ni derivative of a N4macrocyclic

  有人提出，辅酶F430（1）的甲基镍（II）衍生物可作为甲基CoM还原酶催化的酶促过程的中间体。间接证据表明，F30M 1（从F430M II（2）获得）与亲电子的甲基供体反应形成CH 3 –F430M II。此处给出的结果表明确实存在这样的化合物。通过用（CD 3）2原位甲基化制备辅酶F430的五甲酯2（F430M）的顺磁CD 3 -Ni II衍生物5b镁，其特征是各向同性的2 H-NMR光谱。在-40°处，发现轴向配位的CD 3基团的非常宽的D信号在-490ppm处。与甲基（四甲基环己基）镍（II）衍生物4（[Ni II（CH 3））（tmc）] CF 3 SO 3（4a）的2 H-和1 H-NMR谱图进行比较是唯一分离出的CH 3 – N 4大环Ni II的Ni衍生物络合物”表明，向电场的大的各向同性位移是轴向键合到Ni中心的Me基团的特征。的C的各向同性转变温度依赖性d 3 -Ni组中同时4B和5B如下居里定律和产量2
• Saez, Isabel M.; Meanwell, Neil J.; Nutton, Andrew, Journal of the Chemical Society, Dalton Transactions, 1986, p. 1565 - 1576
  作者：Saez, Isabel M.、Meanwell, Neil J.、Nutton, Andrew、Isobe, Kiyoshi、Miguel, Amelio Vazquez de、et al.

  DOI：——

  日期：——
• Dialkyl-μ-ethylidene-μ-methylene-bis(pentamethylcyclopentadienyl)-dirhodium complexes: synthesis, spectra and decomposition reactions
  作者：Zhi-Qiang Wang、Jesús Martínez、Peter M. Maitlis

  DOI：10.1016/s0020-1693(98)00054-1

  日期：1998.10

  The dialkyl-mu-ethylidene-mu-methylene-bis(pentamethylcyclopentadienyl)-dirhodium complexes [(C5Me5)Rh}(2)(mu-CH2) (mu-CHMe)-(R)(2)] (4, R = Me; 5, Et; 6, n-Bu; 7, CH=CH2; and 8, Z-CH=CHMe) have been prepared from RMgBr and [(C5Me5)Rh}(2)(mu-CH2)-(mu-CHMe) (X)(2)] (2, X = Cl; 3, X = Br). Structures deduced from the NMR spectra show that the dialkyl complexes can exist In one trans and two cis forms. The decomposition of the dimethyl complex 4 is compared with that of the related di-mu-methylene complex; it reacts readily (30 degrees C, MeCN solution) in the presence of one-electron oxidisers to give propene and methane and a Little ethene and some butenes. Mass-spectrometric analysis of the C-13 labelling in the organics originating from [(C5Me5)Rh}(2)(mu-CH2) (mu-CHMe) ((CH3)-C-13)(2)] shows that methane derives from the Rh-Me, ethene half from the ethylidene and half from coupling of Rh-methyl and a bridging methylene, while the propene arises almost entirely from the ethylidene and a rhodium methyl. The butenes come from coupling of ethylidene, methylene and a Rh-methyl, but only quite small amounts are formed; thus C + C coupling is the major decomposition path for the mu-ethylidenes, in contrast to the di-mu-methylene complexes where C + C + C coupling predominates. The divinyl complex [(C5Me5)Rh}(2)(mu-CH2) (mu-CHMe)-(CH=CH2)(2)] also underwent internal C + C coupling on reaction with AgBF4 in MeCN to give a mixture of the allyl and methylallyl cations [(C5Me5)Rh(eta(3)-CH2CHCHR) (MeCN)](divided by) (10, R = H; 11, R = Me). (C) 1998 Elsevier Science S.A. All rights reserved.