[1-(Bis-trimethylsilanyl-methyl)-2,2-dimethyl-prop-(E)-ylidene]-trimethylsilanyl-amine | 190847-65-5

• 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-(Bis-trimethylsilanyl-methyl)-2,2-dimethyl-prop-(E)-ylidene]-trimethylsilanyl-amine
• CAS: 190847-65-5
• 化学式: C₁₅H₃₇NSi₃
• 分子量: 315.722
• InChiKey: YICFWOGERXQOIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.89
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [1-(Bis-trimethylsilanyl-methyl)-2,2-dimethyl-prop-(E)-ylidene]-trimethylsilanyl-amine 在 hydrochloric acid diethyl ether 作用下， 以 乙醚 为溶剂， 反应 0.5h， 生成 1-(Bis-trimethylsilanyl-methyl)-2,2-dimethyl-propylideneamine
  参考文献：
  名称：

  The Mechanism of Methane Elimination in B(C₆F₅)₃-Initiated Monocyclopentadienyl-Ketimide Titanium and Related Olefin Polymerization Catalysts

  摘要：

  A new class of monocyclopentadienyl titanium olefin polymerization catalysts and their activation with B(C6F5)(3) is reported herein. Dichlorides Cp[Bu-t(R)C=N]TiCl2 {Cp = C5H5, R = Bu-t (1a); Cp = C5Me5, R = Bu-t (2a); Cp = C5Me4SiMe3, R = Bu-t (3a); Cp = C5Me5, R = CH2SiMe3 (4a); Cp = C5Me5, R = Me (5a)} were prepared in 50-92% yield from CpTiCl3 and Bu-t(R)C=NLi. Analogous dimethyl compounds 1b-5b were prepare via methylation of dichlorides a using MeMgBr in 89-92% yield. Dimethyl compound 6b (L = C5Me5, R = CH(SiMe3)(2)) was prepared directly from Cp*TiMe3 and Bu-t[(Me3Si)(2)CH]C=NH in 40% yield. Dynamic H-1 NMR studies showed that the ketimide ligands in compounds b rotate rapidly about Ti-N on the NMR time scale, with a a Delta G(double dagger) of 9.6(6) kcal mol(-1) or less. The mixed alkyl compound Cp*-[Bu-t(R)C=N]Ti(CH3)CH2SiMe3 {R = (t)3u (7)} was prepared via alkylation of the corresponding methyl chloride derivative with BrMgCH2SiMe3. When treated with B(C6F5)(3), compounds 1b-6b are rapidly converted into the ion pairs {Cp[Bu-t(R)C=N]TiCH3}(+)[H3C(B(C6F5)(3)](-), 1c-6c; mixed alkyl compound 7 yields the ion pair [Cp*((Bu2C)-Bu-t=N)TiCH2SiMe3](+)[H3C(B(C6F5)(3)](-), 7c, exclusively. Multinuclear NMR experiments show that ion pairing is tight in these compounds and that ketimide ligand rotation is occurring with a slightly higher barrier in comparison to the neutral derivatives b. Ion pairs 1c-5e undergo a decomposition process involving loss of methane and producing the neutral compounds Cp[Bu-t(R)C=N]Ti(C6F5)[CH2B(C6F5)(2)], 1d-5d. The X-ray crystal structure of Id has been determined. Active cationic compounds are not regenerated from neutral compounds d in the presence of B(C6F5)(3) and thus this reaction is a potential deactivation pathway for these particular ion pairs. Detailed kinetic studies on the decomposition of 2c show the reaction to be first order in [2c] with activation parameters of Delta H-double dagger = 20.6(8) kcal mol(-1) and Delta S-double dagger = -8.5(10) eu, corresponding to Delta G(298)(double dagger) of 23.1(8) kcal mol(-1). A substantial kinetic isotope effect of k(H)/k(D) = 9.1(6) was measured using d(6)-2c. Further mechanistic experiments, including crossover and examination of alkane elimination from mixed alkyl ion pair 7c, point to a sigma-bond metathesis mechanism for the production of compounds d. The implications of our results for other, related catalyst systems are discussed.

  DOI：

  10.1021/ja994378c
• 作为产物：
  描述：

  三氟甲磺酸三甲基硅酯 、 lithium;[(E)-3,3-dimethyl-1-trimethylsilylbut-1-en-2-yl]-trimethylsilylazanide 以 正戊烷 为溶剂， 以92%的产率得到[1-(Bis-trimethylsilanyl-methyl)-2,2-dimethyl-prop-(E)-ylidene]-trimethylsilanyl-amine
  参考文献：
  名称：

  Hitchcock, Peter B.; Lappert, Michael F.; Layh, Marcus, Journal of Organometallic Chemistry, 1999, vol. 580, # 2, p. 386 - 398

  摘要：

  DOI：

文献信息

• The role of lithium 1,3-bis(trimethylsilyl)-1-aza-allyls in phosphorus chemistry
  作者：Peter B. Hitchcock、Michael F. Lappert、Marcus Layh

  DOI：10.1016/s0022-328x(96)06601-6

  日期：1997.2

  Treatment of the lithium 1-aza-allyl [LiN(R)C(Bu-t)CHR}](2) 1, abbreviated as [<(Li(L)over bar>L')](2), with PCl3 gave in poor yields the trans-P,P'-dichlorodiazaphosphetidine C<(IPN(R')P(Cl)N)over bar>R' 3 (R=SiMe3, R'=C(Bu-t)=C(H)SiMe3). An improved route to 3 was based on [Cu(mu-LL')}(2)] and PCl3; but the method of choice involved conversion of 1 into successively the imine RN=C(Bu-t)CHR2 4 (which upon heating gave the isomeric enamine 5) and Cl2PN=C(Bu-t)CHR2 6 and thermolysis of 6. The imine RN=C(Bu-t)CH(R)PPh2 7, obtained from [<(Li(L)over bar>L')](2) 1 and Ph2PCl, was isomerised into the Z-enamine R2NC(Bu-t)=C(H)PPh2 8, which upon irradiation gave a mixture of 8 and its E-isomer 9. Treatment of 7 with R '' PCl2 or PCl3 gave the cyclic phosphonium chlorides [Ph-2<(PP(R '')N(H)C(Bu-t)=C)over bar>H]Cl (10 R ''=Ph, or 11 R ''=Et) or [Ph-2<(PP(Cl)N(R)C(Bu-t)=C)over bar>H]Cl 12; 12 with AgOSO2CF3 or Na[BPh4] afforded [Ph-2<(PP(Cl)N(R)C((BU)-B-t)=C)over bar>H]A (13 A=CF3SO3, or 14 A=BPh4). The enamines RN=C(Bu-t)CH(X)R (15 X=Cl, or 16 X=I) were obtained from 1 and POCl3 or ICI respectively, and the enamine R2NC(Ph)=CR2 17 was obtained from the lithium 1-aza-allyl[Li(N(R)C(Ph)CR2)(THF)] and CF3SO3SiMe3. Compounds 3-17 were characterised by multinuclear NMR spectroscopy and (in most cases) MS; while single crystal X-ray diffraction data are provided for 3 and 10.