di(methyl-13C)magnesium | 106722-72-9

• 分子结构分类: 有机化合物
• 英文名称: di(methyl-13C)magnesium
• CAS: 106722-72-9
• 化学式: C₂H₆Mg
• 分子量: 56.3526
• InChiKey: KZLUHGRPVSRSHI-ISOLYIDJSA-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：
  0.0
• 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：

  di(methyl-13C)magnesium 、 (N[2-PⁱPr₂-4-methylphenyl]₂)NbCl₂(O-2,6-ⁱPr₂C₆H₃) 以 四氢呋喃 、 1,4-二氧六环 、 甲苯 为溶剂， 反应 3.0h， 以88%的产率得到(N[2-PⁱPr₂-4-methylphenyl]₂)Nb(¹³CH₃)₂(O-2,6-ⁱPr₂C₆H₃)
  参考文献：
  名称：

  末端结合铌甲基炔

  摘要：

  配合物 (PNP)Nb(CH3)2(OAr) (PNP = N[2-P(i)Pr2-4-methylphenyl]2(-), Ar = 2,6-(i)Pr2C6H3)，由处理(PNP)NbCl3 与 NaOAr 和 2 当量的 H3CMgCl，可以用 [FeCp2][OTf] 氧化得到 (PNP)Nb(CH3)2(OAr)(OTf)。虽然后者的光解导致形成了一个罕见的亚甲基铌例子，(PNP)Nb=CH2(OAr)(OTf)，但用叶立德 H2CPPh3 处理三氟甲磺酸二甲酯前体产生了单核第 5 基亚甲基配合物，（PNP )Nb≡CH(OAr)。将布朗斯台德碱添加到 (PNP)Nb=CH2(OAr)(OTf) 也导致形成亚甲基。固态结构分析证实亚甲基和亚甲基部分都是末端，具有非常短的 Nb-C 距离，分别为 1.963(2) 和 1.820(2) Å。

  DOI：

  10.1021/jacs.6b00830

文献信息

• Maitlis, Peter M., Pure and Applied Chemistry, 1989, vol. 61, p. 1747 - 1754
  作者：Maitlis, Peter M.

  DOI：——

  日期：——
• 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.
• The Dynamics of the β-Agostic Isopropyl Complex (ArNC(R)−C(R)NAr)Pd(CH(CH₂-μ-H)(CH₃))⁺BAr₄‘^- (Ar = 2,6-C₆H₃(<i>i</i>-Pr)₂):  Evidence for In-Place Rotation versus Dissociation of the Agostic Methyl Group
  作者：Daniel J. Tempel、Maurice Brookhart

  DOI：10.1021/om971137+

  日期：1998.5.1

  Variable-temperature H-1 and C-13 NMR spectroscopy has been used to study the dynamics of the beta-agostic isopropyl complex (ArN=C(R)-C(R)=NAr)Pd(CH(CH2-mu-H)(CH3))+BAr4'(-) (Ar = 2,6-C6H3(i-Pr)(2)). H-1 and C-13 line shape analysis suggests two independent processes occur: interchange of the agostic and nonagostic methyl groups and exchange of hydrogens within the agostic methyl group, which is best regarded as in-place methyl group rotation. Barriers for both of these processes are similar, with Delta G double dagger ca. 9 kcal/mol. The methyl groups undergo interchange without inversion at the Pd(II) center.