1-trimethylsiloxy-2,2,2-trifluoroacetone dimethylhydrazone | 91152-82-8

• 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-trimethylsiloxy-2,2,2-trifluoroacetone dimethylhydrazone
• 英文别名: Trimethylsilyl 2,2,2-trifluoro-N,N-dimethylethanehydrazonate；trimethylsilyl 2,2,2-trifluoro-N,N-dimethylethanehydrazonate
• CAS: 91152-82-8
• 化学式: C₇H₁₅F₃N₂OSi
• 分子量: 228.29
• InChiKey: PJHNGRWNXQSVQJ-UHFFFAOYSA-N

物化性质

• 沸点：
  143.3±50.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.28
• 重原子数：
  14
• 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：
  6

反应信息

• 作为反应物：
  描述：

  1-trimethylsiloxy-2,2,2-trifluoroacetone dimethylhydrazone 在 四氯化硅 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以100%的产率得到bis(N-(dimethylamino)fluoroacetimidato-N,O)dichlorosilicon(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
• 作为产物：
  描述：

  三甲基氯硅烷 、 Trifluoro-acetic acid N',N'-dimethyl-hydrazide 在 三乙胺 作用下， 以 苯 为溶剂， 以90%的产率得到1-trimethylsiloxy-2,2,2-trifluoroacetone dimethylhydrazone
  参考文献：
  名称：

  Kalikhman, I. D.; Medvedeva, E. N.; Bannikova, O. B., Journal of General Chemistry of the USSR, 1984, vol. 54, # 2, p. 426 - 427

  摘要：

  DOI：

文献信息

• (Iodomethyl)fluorosilanes: Synthesis and Reactions
  作者：B. А. Gostevskii、N. F. Lazareva

  DOI：10.1134/s1070363218100092

  日期：2018.10

  The methods of synthesis of bifunctional (iodomethyl)fluorosilanes of general formula ICH2SiMenF3–n (n = 0, 2) have been elaborated; the structure was proved by 1H, 13C, 29Si NMR spectroscopy. The reaction of (iodomethyl)dimethylfluorosilane with O-trimethylsilyl derivative of N,N'-dimethylhydrazide of trifluoroacetic acid gives rise to the formation of 2,2,4,4-tetramethyl-6-(trifluoromethyl)-3,4-dihydro-2Н-1

  阐述了合成通式ICH 2 SiMe n F 3– n（n = 0，2 ）的双官能（碘甲基）氟硅烷的方法；结构通过1 H，13 C，29 Si NMR光谱证实。（碘甲基）二甲基氟硅烷与三氟乙酸的N，N'-二甲基酰肼的O-三甲基甲硅烷基衍生物反应，形成2,2,4,4-四甲基-6-（三氟甲基）-3,4-二氢- 2 Н -1,4,5,2-oxadiasilin -4-鎓碘化物与四配位硅原子上。
• 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。
• Tautomeric Equilibrium between Penta- and Hexacoordinate Silicon Chelates. A Chloride Bridge between Two Pentacoordinate Silicons
  作者：Inna Kalikhman、Olga Girshberg、Lutz Lameyer、Dietmar Stalke、Daniel Kost

  DOI：10.1021/ja004118r

  日期：2001.5.1

  an unexpected equilibrium mixture, 10a right arrow over left arrow 11a, between a neutral hexacoordinate silicon chelate with a covalent chloro ligand (10a) and an ionic pentacoordinate silicon complex (11a). The equilibrium reaction consists formally of a migration of the covalent chloro ligand from silicon to an adjacent ammonium nitrogen, as a chloride anion, and thus constitutes a novel type of

  O-三甲基甲硅烷基-1,1-二甲基-2-三氟乙酰肼 (1a) 与氯甲基（甲基）二氯硅烷的反应提供了出乎意料的平衡混合物，10a 右箭头超过左箭头 11a，在中性六配位硅螯合物与共价氯配体之间(10a) 和离子五配位硅络合物 (11a)。平衡反应形式上包括共价氯配体从硅迁移到相邻的铵氮，作为氯阴离子，因此构成了一种新型的互变异构反应。晶体学和核磁共振数据为反应提供了证据。讨论了温度、溶剂、取代基和反离子对互变异构平衡的影响：当混合物温度升高时，平衡比 10a/11a 增加。在甲苯中形成混合物，非电离溶剂，使平衡完全向中性 10a 移动。当初始酰肼具有苯基 (11c) 或氢 (11b) 基团作为取代基而不是 CF3 时，平衡向离子侧移动。使用三氟甲磺酸三甲基甲硅烷基酯用三氟甲磺酸酯代替氯化物反离子，将 10a/11a 混合物转移到离子侧。对 10/11 的逐步形成进行了低温 NMR 监测，并提供了对反应机理的深入了解。在尝试生长
• Facile central-element exchange in neutral hexacoordinate germanium and silicon complexes; synthesis and characterization of germanium complexes
  作者：Shiri Yakubovich、Inna Kalikhman、Daniel Kost

  DOI：10.1039/c0dt00625d

  日期：——

  Neutral hexacoordinate germanium complexes with hydrazido chelating ligands have been synthesized and characterized. Facile exchange of central element between silicon and germanium in these complexes is demonstrated, following given selectivity constraints.

  中性六坐标 锗 与复合物 肼基多螯合配体已经合成和表征。中心元素之间的轻松交换硅 和 锗 在给定的选择性约束条件下，证明了这些配合物中的二甲双胍。
• Crystal Structures and Stereodynamics of Neutral Hexacoordinate Silicon Chelates:  Use of an Optically Active Ligand for Assignment of an Intramolecular Ligand Exchange Process
  作者：Daniel Kost、Inna Kalikhman、Sonia Krivonos、Dietmar Stalke、Thomas Kottke

  DOI：10.1021/ja9730021

  日期：1998.5.1

  Crystal structures determined for several neutral hexacoordinate bis(N-->Si) chelates revealed in all cases near octahedral geometries with the nitrogen ligands in relative trans and the monodentate Ligands in cis positions. To assign the two consecutive intramolecular ligand-site exchange processes (reported earlier), a bis-chelate was prepared containing a chiral carbon center in each of the chelate rings (14). By means of a phase sensitive NOESY NMR spectrum it was possible to conclude that the lower-barrier process involved exchange of diastereotopic groups only within each diastereomer, and not between them, resulting in the assignment of this process to the direct nondissociative interchange of the monodentate ligands (X, Y). The Si-Cl bond lengths were found to inversely correlate with the lower of the activation barriers. Dissociation-recombination of-the N-->Si dative bond was also observed by the high-temperature NMR spectra. Lack of correlation between Si-N distances in the crystals and activation barriers led to the conclusion that Si-N dissociation was not involved in the measured rate processes, but followed, at slightly higher temperature, the epimerization at the silicon center by exchange of the two oxygen sites.