bis(N-(dimethylamino)acetimidato-N,O)chloro(phenyl)silicon(IV)

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(N-(dimethylamino)acetimidato-N,O)chloro(phenyl)silicon(IV)
• 英文别名: [chloro-[(Z)-N-(dimethylamino)-C-methylcarbonimidoyl]oxy-phenylsilyl] (1Z)-N,N-dimethylethanehydrazonate
• 化学式: C₁₄H₂₃ClN₄O₂Si
• 分子量: 342.901
• InChiKey: RWHOZKJGHTXOPY-MCOFMCJXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.89
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  49.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  bis(N-(dimethylamino)acetimidato-N,O)chloro(phenyl)silicon(IV) 以 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  通过 Si-Cl 键的快速解离-重组在中性六配位硅配合物和离子五配位硅盐之间实现平衡

  摘要：

  通过低温29Si NMR观察到中性六配位硅配合物和离子型氯化硅之间的平衡，这种平衡是高温、溶剂、抗衡离子、配体和取代基依赖性的，通过低温29Si NMR观察并通过晶体分析证实。

  DOI：

  10.1039/b102427m
• 作为产物：
  描述：

  苯基三氯硅烷 、 1,1-dimethyl-2-(α-trimethylsiloxy)ethylene hydrazine 生成 bis(N-(dimethylamino)acetimidato-N,O)chloro(phenyl)silicon(IV)
  参考文献：
  名称：

  Stereodynamics of neutral six-coordinate silicon chelates: evidence for two non-dissociative rate processes

  摘要：

  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。

  DOI：

  10.1039/c39950001253

文献信息

• Low-temperature ionization of neutral hexacoordinate to ionic pentacoordinate silicon complexes. Unusual temperature, solvent and substituent effects
  作者：Daniel Kost、Inna Kalikhman、Vijeyakumar Kingston、Boris Gostevskii

  DOI：10.1002/poc.551

  日期：2002.12

  Neutral hexacoordinate complexes of silicon (1) ionize to pentacoordinate siliconium chloride salts (2) in CH2Cl2, CHCl3 or CHFCl2 solutions. 29Si NMR measurements prove that the extent of ionization increases as the temperature of the solution is lowered. The ionizations are slightly exothermic, and have negative entropies. It is shown that increased solvent polarity drives the reaction to the ionic

  硅（1）的中性六配位络合物在CH 2 Cl 2，CHCl 3或CHFCl 2溶液中电离成五配位氯化硅盐（2）。29 Si NMR测量证明，电离的程度随着溶液温度的降低而增加。电离略微放热，并且具有负熵。已显示出增加的溶剂极性将反应驱动至离子侧，即离子溶剂化导致离子化。添加四丁基氯化铵缺乏共离子效应表明形成了未分离的离子对。版权所有©2002 John Wiley＆Sons，Ltd.
• 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.