tris(tert-butyl)silylamine lithium salt | 82135-42-0

• 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: tris(tert-butyl)silylamine lithium salt
• 英文别名: tri-tert-butylSiNHLi；t-Bu3SiNHLi；lithium;tritert-butylsilylazanide
• CAS: 82135-42-0
• 化学式: C₁₂H₂₈LiNSi
• 分子量: 221.388
• InChiKey: XNRACMFHHVIELU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.39
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tris(tert-butyl)silylamine lithium salt 在 CH₃MgBr 作用下， 以 乙醚 为溶剂， 生成 methyltris((tri-tert-butylsilyl)amino)zirconium
  参考文献：
  名称：

  Cummins, Christopher C.; Van Duyne, Gregory D.; Schaller, Christopher P., Organometallics, 1991, vol. 10, # 1, p. 164 - 170

  摘要：

  DOI：
• 作为产物：
  描述：

  tri-t-butylsilane 在 lithium amide 、 甲基锂 作用下， 以 四氢呋喃 、 乙醚 、 正庚烷 为溶剂， 反应 48.0h， 生成 tris(tert-butyl)silylamine lithium salt
  参考文献：
  名称：

  Supersilyliertes Ammoniak und supersilyliertes Hydrazin: Synthese, Struktur und Eigenschaften / Supersilyl Ammonia and Supersilyl Hydrazine: Synthesis, Structure and Properties

  摘要：

  一种优异的超硅基化剂，超硅基三氟甲磺酸酯，tBu₃SiO₃SCF₃，可通过tBu₃SiH和CF₃SO₃H轻松获得。超硅基三氟甲磺酸酯，tBu₃SiO₃SCF₃，与锂酰胺或锂肼反应，形成超硅基胺，tBu₃SiNH₂，或超硅基肼，tBu₃SiNHNH₂和tBu₃SiNH-HNSitBu₃。超硅基三氟甲磺酸酯，tBu₃SiO₃SCF₃，和双超硅基肼，tBu₃SiNH-HNSitBu₃的结构已通过X射线结构分析确定。

  DOI：

  10.1515/znb-2002-0208

文献信息

• Synthesis of (^tBu₃SiNH)₂ClW⋮WCl(NHSi^tBu₃)₂ and Its Degradation via NH Bond Activation
  作者：Stephen M. Holmes、Daniel F. Schafer、Peter T. Wolczanski、Emil B. Lobkovsky

  DOI：10.1021/ja010957h

  日期：2001.10.31

  NaW2Cl7(THF)5 with 4 equiv of (t)Bu3SiNHLi afforded the C2 W(III) dimer [((t)Bu3SiNH)2WCl]2 (1, d(W triple bond W) = 2.337(2) A), which is a rare, primary amide M2X4Y2 species. Its degradation provided evidence of NH bond activation by the ditungsten bond. Addition of 2 equiv of (t)Bu3SiNHLi or TlOSi(t)Bu3 to 1 yielded H2 and hydride ((t)Bu3SiN)2((t)Bu3SiNH)WH (2, d(WH) = 1.67(3) A) or ((t)Bu3SiN)2((t)Bu3SiO)WH

  用 4 当量的 (t)Bu3SiNHLi 处理 NaW2Cl7(THF)5 得到 C2 W(III) 二聚体 [((t)Bu3SiNH)2WCl]2 (1, d(W 三键 W) = 2.337(2) A) ，这是一种罕见的伯酰胺 M2X4Y2 物种。它的降解提供了二钨键激活 NH 键的证据。将 2 当量的 (t)Bu3SiNHLi 或 TlOSi(t)Bu3 添加到 1 生成 H2 和氢化物 ((t)Bu3SiN)2((t)Bu3SiNH)WH (2, d(WH) = 1.67(3) A) 或((t)Bu3SiN)2((t)Bu3SiO)WH (3)。1 in py 的热解 (60 摄氏度, 16 小时) 得到 ((t)Bu3SiN)2WHCl(py) (4-py, 40-50%), ((t)Bu3SiN)2WCl2(py) (6-py, 10%) 和 ((t)Bu3SiN)2HW(mu-
• Ethylene Polymerization with Half-Sandwich Allyl Imido Complexes of Tantalum
  作者：David M. Antonelli、Ann Leins、Jeffrey M. Stryker

  DOI：10.1021/om9703494

  日期：1997.6.1

  The imido-based half-sandwich complex Cp*Ta(N(2,6-diisopropylphenyl))(η1-C3H5)(η3-C3H5) (3) polymerizes ethylene in the presence of [(C6H5)3C]+[(C6F5)4B]- or B(C6F5)3, while chloride and alkyl derivatives are inactive in the presence of MAO or alkyl abstraction reagents. In contrast, however, Cp*Ta(NSi(tert-butyl)3)Cl2 (5) polymerizes ethylene in the presence of MAO while Cp*Ta(NSi(tert-butyl)3)(η1-C3H5)(η3-C3H5)

  基于酰亚胺半夹心络合物的Cp * TA（N（2,6-二异丙基））（η 1 -C 3 ħ 5）（η 3 -C 3 H ^ 5）（3）聚合中的存在下进行[乙烯（ C 6 H 5）3 C] + [（C 6 F 5）4 B] -或B（C 6 F 5）3，而氯化物和烷基衍生物在MAO或烷基提取试剂的存在下是无活性的。相反，Cp * TA（NSi（叔丁基）3）Cl2（5）聚合乙烯在MAO存在下，同时的Cp * TA（NSI（叔丁基）3）（η 1 -C 3 ħ 5）（η 3 -C 3 H ^ 5）（6）1和Cp * TA（NSi（叔丁基）3）Me 2（4）在烷基抽象剂的存在下基本上是无活性的。
• Selectivities in Hydrocarbon Activation:  Kinetic and Thermodynamic Investigations of Reversible 1,2-RH-Elimination from (silox)₂(^tBu₃SiNH)TiR (silox = ^tBu₃SiO)
  作者：Jordan L. Bennett、Peter T. Wolczanski

  DOI：10.1021/ja9707419

  日期：1997.11.1

  Addition of 2.0 equiv of Na(silox) to TiCl4(THF)(2) afforded (silox)(2)TiCl2 (1), which yielded (silox)(2)((Bu3SiNH)-Bu-t)TiCl (2-Cl) upon treatment with (Bu3SiNLi)-Bu-t. Grignard or alkyllithium additions to 2-Cl or 1,2-RH-addition to transient (silox)(2)Ti=(NSiBu3)-Bu-t (3) produced (silox)(2)((Bu3SiNH)-Bu-t)TiR (2-R; R = Me, Et, CH2Ph = Bz, CH=CH2 = Vy, Bu-c, Bu-n, Ph, H, Pr-c, (c)Pe, CH2-3,5-Me2C6H3 = Mes, (neo)Hex, (c)Hex, eta(3)-H2CHCH2, eta(3)-H2CCHCHMe). Insertions of C2H4, butadiene, HC2H, and (HC2Bu)-Bu-t into the titanium-hydride bond of 2-H generated (silox)(2)((Bu3SiNH)-Bu-t)TiR (2-R; R = Et, eta(3)-H2CCHCHMe, Vy, E-CH=(CHBu)-Bu-t). Trapping of 3 by donors L afforded (silox)(2)LTi=(NSiBu3)-Bu-t (3-L; L = OEt2, THF (X-ray, two independent molecules: d(Ti=N) = 1.772(3), 1.783(3) Angstrom), py, PMe3, NMe3, NEt3) and metallacycles (silox)(2)((Bu3SiN)-Bu-t)TiCR=CR' (3-RC2R'; RC2R' = HC2H, MeC2Me, EtC2Et, (HC2Bu)-Bu-t) and (silox)(2)((Bu3SiN)-Bu-t)TiCH2CH2 (3-C2H4). Kinetics of 1,2-RH-elimination from 2-R revealed a first-order process (24.8 degrees C): R = Bz < Mes < H < Me (1.54(10) x 10(-5) s(-1)) < (neo)Hex < Et < Bu-n < Bu-c < (c)Pe < (c)Hex < Pr-c < Vy < Ph. Kinetics data, large 1,2-RH/D-elimination KIE's (e.g., MeH/D, 13.7(9), 24.8 degrees C), and Eyring parameters (e.g., 2-Me, Delta H double dagger = 20.2(12) kcal/mol, Delta S double dagger = -12(4) eu) portray a four-center, concerted transition state when the N ... H ... R linkage is nearly linear. Equilibrium measurements led to the following relative standard free energy scale: 2-(c)Hex > 2-(c)Pe > 2-Pr-n similar to 2-Bu-n > 2-(neo)Hex > 2-Et, 2-Bu-c > 2-CH2SiMe3 > 2-Ph > 2-Me > 2-Bz > 2-Pr-c similar to 2-Mes > 2-Vy > 3-C2H4 > 3-NEt3 > 2-H > 3-OEt2 > 3-EtC2Et > 3-MeC2Me > 3-THF > 3-NMe3 > 3-PMe3 > 3-py. A correlation of D(TiR)(rel) to D(RH) revealed greater differences in titanium-carbon bond energies. THF loss from 3-THF allowed a rough estimate of Delta G degrees(3). Using thermochemical cycles, relative activation energies for 1,2-RH-addition were assessed: (c)HexH > (c)PeH > (BuH)-Bu-n > (neo)HexH > EtH > BzH > (BuH)-Bu-c > MesH > MeH > PhH > (PrH)-Pr-c > VyH > 3-C2H4 formation > H-2. On the basis of a parabolic model, C-H bond activation selectivities are influenced by the relative ground state energies of 2-R and a parameter representing the reaction coordinate. A more compressed reaction coordinate for sp(2)- vs sp(3)-substrates eases their activation.
• With, Jan de; Horton, Andrew D., Angewandte Chemie, 1993, vol. 105, p. 958 - 960
  作者：With, Jan de、Horton, Andrew D.

  DOI：——

  日期：——
• Hydrocarbon Activation via Reversible 1,2-RH-Elimination from (^tBu₃SiNH)₃ZrR:  Synthetic, Structural, and Mechanistic Investigations
  作者：Christopher P. Schaller、Christopher C. Cummins、Peter T. Wolczanski

  DOI：10.1021/ja950745i

  日期：1996.1.1

  Hydrocarbyl complexes, ((t)Bu(3)SiNH)(3)ZrR (1-R), were prepared via metatheses of ((t)Bu(3)SiNH)(3)ZrCl (1-Cl) with RMgX or RLi (R = Me, Et, Cy, CH(2)Ph, allyl, CH=CH2, Ph, CH(2)(t)Bu, C=CPh, C=C(t)Bu), through addition of isobutylene, H2C=C=CMe(2), and acetylene to 1-H (R = (i)Bu, dma, or CH=CH2), and by CH-bond activation; thermal 1,2-RH-elimination from 1-R produced putative ((t)Bu(3)SiNH)(2)Zr=NSi(t)Bu(3) (2), which was subsequently trapped by R'H. Thermolysis of 1-R (similar to 100 degrees C, R = Me or Cy) in the presence of H-2, c-C3H6, and CH4 in cyclohexane or neat C6H6, mesitylene, and toluene afforded 1-R (R = ii, Pr-c, Me, Ph, CH2-3,5-Me(2)C(6)H(3)) and a mixture of 1-CH(2)Ph and 1-C(6)H(4)Me, respectively. Exposure of 1-Cy to C2H4 or C6H6 in cyclohexane provided 1-CH=CH2 or 1-Ph, respectively, but further reaction produced 1(2)-(trans-HC=CH) and 1(2)-(p-C6H4) through double CH-bond activation. Thermolysis of ((t)Bu(3)SiND)(3)ZrCH3 (1-(ND)(3)-CH3) in C6H6 or C6D6 yielded CH3D, and 1C(6)H(5) or 1-(ND)(3)C6D5, through reversible benzene activation. Thermolysis of l-Cy in neat cyclohexane, and with C2H6 Or CMe(4) present, gave cyclometalation product ((t)Bu(3)SiNH)(2)ZrNHSi(t)Bu(2)CMe(2)CH(2) (3) and 1-NHSi(t)Bu(3). In THF, thermolysis of 1-CH3 afforded ((t)Bu(3)SiNH)(2)-(THF)Zr=NSi(t)Bu(3) (2-THF); at 25 degrees C, 1-H lost H-2 in the presence of L (L = THF, Et(2)O, NMe(3), PMe(3)) generating 2-L; 2-L (L = Et(2)O py) was also prepared via ligand exchange with 2-THF. Single crystal X-ray diffraction studies of 2-THF revealed a pseudotetrahedral core, with a long Zr=N bond distance (1.978(8) Angstrom), normal Zr-N(H) bond lengths (2.028(8), 2.031(8) Angstrom, similar amide (154.7(5), 158.1(5)degrees) and imide (156.9(5)degrees) bond angles, and little O(p pi) --> Zr(d pi) bonding. Crystal data: monoclinic, P2(1)/n, a = 13.312(5) Angstrom, b = 18.268(6) Angstrom, c = 20.551(7) Angstrom, beta = 92.30(3)degrees, Z = 4, T = 25 degrees C. 2-Et(2)O thermally eliminated C2H4 to give 1-OEt through gamma-CH activation. Kinetic isotope effects (KIE) on 1,2-RD-elimination from 1-(ND)(3)-R (95.7 degrees C, R = CH3, z(Me) = 6.3(1); CH(2)Ph, z(Bz) = 7.1(6); Ph, z(Ph) = 4.6(4)) and CD3H loss from 1-CD3((CH3)/k(CD3) = (z'(Me))(3) = 1.32) revealed a symmetric H-transfer in a loose transition state. 1,2-RH-elimination rates follow: (96.7 degrees C, k(R) (x10(4) s(-1)) = 22.6(2), Ph; 15.5(2), Pr-c; 13.2(4), CH=CH2; 10.4(2), Cy; 3.21(6), Et; 3.2(1), (i)Bu; 1.3(1), dma; 1.51(6), H; 1.42(4), CH(2)(t)Bu; 1.06(2), Me; 0.34(2), CH2-3,5-Me(2)C(6)H(3); 0.169(3), CH(2)Ph).Competition for ((t)Bu(3)SiNH)(2)Zr=NSi(t)Bu(3) (2) by RH/R'H and equilibria provided information about the stabilities of 1-R relative to 1-Pr-c (R = CPr (0.0 kcal/mol) < Ph (0.3) < CH(2)Ph (0.7) < Me (1.2) < CH(2)(t)Bu (greater than or equal to 7.6) < Et (greater than or equal to 7.8) < Cy (greater than or equal to 10.9)). Transition state energies afforded relative C-H bond activation selectivities (Delta Delta G double dagger relative to Pr-c-H): (PrH)-Pr-c approximate to ArH (0.0 kcal/mol) > MeH (3.4) > PhCH(2)H (4.0) > cyclometalation (greater than or equal to 8.5) > EtH(greater than or equal to 8.9) > (t)BuCH(2)H (greater than or equal to 9.3) > CyH (greater than or equal to 11.2). A correlation of Delta G double dagger(1,2-RH-elimination) with D(R-H) indicated generally late transition states but suggested an earlier composition for the alkyls, as rationalized through a Hammond analysis. Correlation of Delta G double dagger(1,2-RH-elimination) with RH proton affinity implicated tight binding of RH in the transition state and possible RH-binding intermediates (2-RH). 1,2-HC=CR-elimination from 1-C=CR was not observed, but second-order exchanges of 1-C=CPh with (t)BuC=CH, and 1-C=C(t)Bu with HC=CPh were indicative of an associative pathway. All data can be accommodated by the following mechanism: 1-R + R'H reversible arrow 2-RH + R'H reversible arrow 2-R'H + RH reversible arrow 1-R' + RH; a variant where 2 mediates reversible 2-RH + R'H exchange is less likely.