1,1-dimethyl-2-(α-trimethylsiloxy)ethylene hydrazine | 171566-32-8

• 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: 1,1-dimethyl-2-(α-trimethylsiloxy)ethylene hydrazine
• 英文别名: Trimethylsilyl N,N-dimethylethanehydrazonate；trimethylsilyl N,N-dimethylethanehydrazonate
• CAS: 171566-32-8
• 化学式: C₇H₁₈N₂OSi
• 分子量: 174.318
• InChiKey: XUKIVMQMUVFWDC-UHFFFAOYSA-N

物化性质

• 沸点：
  168.5±23.0 °C(Predicted)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.73
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  24.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,1-dimethyl-2-(α-trimethylsiloxy)ethylene hydrazine 在 三氯硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以97%的产率得到bis(N-(dimethylamino)acetimidato-N,O)chlorohydridosilicon(IV)
  参考文献：
  名称：

  Neutral Hexacoordinate Silicon Complexes. Synthesis, Structure, and Stereodynamics: Evidence for Two Nondissociative Ligand-Exchange Mechanisms

  摘要：

  Novel hexacoordinate silicon compounds 1-4 with two identical bidentate ligands, respectively, are readily prepared in high yields from the reaction of XSiCl(3) (X = H, Me, Ph, Cl) with the O-trimethylsilyl derivatives of N,N-dimethyl carbohydrazides 6. The NMR spectra of all compounds indicate that a single diastereomer is present in solution, of the possible six, within NMR detection limits. The published X-ray crystallographic structure of one of the complexes, as well as an analysis of the H-1, C-13 and Si-29 NMR spectra and their temperature dependence, conforms to an octahedral geometry with the oxygen ligands and the pair of monodentate ligands cis to each other, respectively, and the nitrogens in a trans position. All of the complexes show temperature dependence of their NMR spectra, characteristic of fluxional behavior. Two rate processes (topomerizations) take place on the NMR time scale in compounds 1-3, at activation free energies ranging, respectively, between 10.6 and 16.4 kcal/mol, and 15.0 and 18.5 kcal/mol. A single process is observed for the C-2v symmetric 4 complexes. A remarkable solvent dependence of barriers is observed, suggesting that ligand site exchange is associated with dissociation or weakening of Si-ligand bonds. The simultaneous exchange of N-methyl groups and benzyl methylene protons in 3d is evidence that no Si-N bond cleavage and chelate ring opening take place during topomerization. The persistence of Si-29-F-19 one-bond coupling, observed in the Si-29 NMR spectrum at temperatures well above the fast exchange limit temperature, proves that no ionic dissociation of the Si-halogen bond takes place. It is concluded that topomerization occurs in a nondissociative, intramolecular Ligand site exchange process. A likely mechanism that accounts for all of these observations is a 1,2-shift of adjacent ligands, X and Cl, or the two oxygen ligands, via a ''bicapped tetrahedron'' intermediate or transition state.

  DOI：

  10.1021/ja00151a015

文献信息

• Stereodynamics of neutral six-coordinate silicon chelates: evidence for two non-dissociative rate processes
  作者：Inna Kalikhman、Daniel Kost、Morton Raban

  DOI：10.1039/c39950001253

  日期：——

  A DNMR spectroscopic study of the Stereodynamics of novel neutral six-coordinate silicon chelates reveals two distinct ligand site exchange processes, both of which are intramolecular non-dissociative.

  对新型中性六配位硅螯合物立体动力学的 DNMR 光谱研究揭示了两种不同的配体位点交换过程，这两种过程都是分子内非解离的。
• Revisiting Methyl-Halide Elimination Reactions in Hydrazide Based Hypercoordinate Silicon(IV) Complexes
  作者：Sannapaneni Janardan、Pothini Suman、Akella Sivaramakrishna、Kari Vijayakrishna

  DOI：10.1080/15533174.2014.988239

  日期：2016.2.1

  of hypercoordinate silicon(IV) complexes are synthesized by the reactions of O-silylated N,N-dimethylhydrazides with YSiCl3 (Y = cyclohexyl and i-Bu). All the complexes are characterized by 1H, 13C, and 29Si-NMR spectroscopy. The influence of steric and electronic behavior of remote substituents and the groups attached to silicon on the methyl halide elimination reactions of these complexes are discussed

  通过O-甲硅烷基化的N，N-二甲基酰肼与YSiCl 3（Y =环己基和i -Bu）反应合成了一组超配位的硅（IV）配合物。所有配合物的特征在于1 H，13 C和29 Si-NMR光谱。讨论了远程取代基和与硅连接的基团的空间和电子行为对这些配合物的甲基卤化物消除反应的影响。甲基卤化物消除的速率强烈依赖于亲核试剂强度（即，I - >溴- >氯- ）和远程取代基R（R =我<吨-Bu
• Kalikhman, I. D.; Bannikova, O. B.; Petukhov, L. P., Doklady Chemistry, 1986, vol. 287, p. 87 - 90
  作者：Kalikhman, I. D.、Bannikova, O. B.、Petukhov, L. P.、Pestunovich, V. A.、Voronkov, M. G.

  DOI：——

  日期：——
• Reaction of o-trimethylsilyl derivatives of 2-acylhydrazines with dimethyl(chloromethyl)chlorosilane
  作者：I. D. Kalikhman、O. B. Bannikova、B. A. Gostevskii、L. I. Volkova、O. A. Vyazankina、N. S. Vyazankin、T. G. Yushmanova、V. A. Lopyrev、M. G. Voronkov、V. A. Pestunovich

  DOI：10.1007/bf00959403

  日期：1987.2
• Neutral Hexacoordinate Silicon Complexes. Synthesis, Structure, and Stereodynamics: Evidence for Two Nondissociative Ligand-Exchange Mechanisms
  作者：Daniel Kost、Inna Kalikhman、Morton Raban

  DOI：10.1021/ja00151a015

  日期：1995.11

  Novel hexacoordinate silicon compounds 1-4 with two identical bidentate ligands, respectively, are readily prepared in high yields from the reaction of XSiCl(3) (X = H, Me, Ph, Cl) with the O-trimethylsilyl derivatives of N,N-dimethyl carbohydrazides 6. The NMR spectra of all compounds indicate that a single diastereomer is present in solution, of the possible six, within NMR detection limits. The published X-ray crystallographic structure of one of the complexes, as well as an analysis of the H-1, C-13 and Si-29 NMR spectra and their temperature dependence, conforms to an octahedral geometry with the oxygen ligands and the pair of monodentate ligands cis to each other, respectively, and the nitrogens in a trans position. All of the complexes show temperature dependence of their NMR spectra, characteristic of fluxional behavior. Two rate processes (topomerizations) take place on the NMR time scale in compounds 1-3, at activation free energies ranging, respectively, between 10.6 and 16.4 kcal/mol, and 15.0 and 18.5 kcal/mol. A single process is observed for the C-2v symmetric 4 complexes. A remarkable solvent dependence of barriers is observed, suggesting that ligand site exchange is associated with dissociation or weakening of Si-ligand bonds. The simultaneous exchange of N-methyl groups and benzyl methylene protons in 3d is evidence that no Si-N bond cleavage and chelate ring opening take place during topomerization. The persistence of Si-29-F-19 one-bond coupling, observed in the Si-29 NMR spectrum at temperatures well above the fast exchange limit temperature, proves that no ionic dissociation of the Si-halogen bond takes place. It is concluded that topomerization occurs in a nondissociative, intramolecular Ligand site exchange process. A likely mechanism that accounts for all of these observations is a 1,2-shift of adjacent ligands, X and Cl, or the two oxygen ligands, via a ''bicapped tetrahedron'' intermediate or transition state.