Na(silox) | 97733-16-9

• 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: Na(silox)
• 英文别名: NaOSi(t)Bu3；Sodium silox；sodium;tritert-butyl(oxido)silane
• CAS: 97733-16-9
• 化学式: C₁₂H₂₇OSi*Na
• 分子量: 238.421
• InChiKey: QAGFKHQOLBYGIF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 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：
  23.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Na(silox) 以 乙醚 为溶剂， 生成 Ti(Me)(OSi-t-Bu3)2(NHSi-t-Bu3)
  参考文献：
  名称：

  Selectivities in Hydrocarbon Activation:  Kinetic and Thermodynamic Investigations of Reversible 1,2-RH-Elimination from (silox)₂(^tBu₃SiNH)TiR (silox = ^tBu₃SiO)

  摘要：

  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.

  DOI：

  10.1021/ja9707419

文献信息

• Pnictogen-Hydride Activation by (silox)₃Ta (silox = ^tBu₃SiO); Attempts to Circumvent the Constraints of Orbital Symmetry in N₂ Activation
  作者：Elliott B. Hulley、Jeffrey B. Bonanno、Peter T. Wolczanski、Thomas R. Cundari、Emil B. Lobkovsky

  DOI：10.1021/ic101147x

  日期：2010.9.20

  Activation of N2 by (silox)3Ta (1, silox = tBu3SiO) to afford (silox)3Ta═N−N═Ta(silox)3 (12-N2) does not occur despite ΔG°cald = −55.6 kcal/mol because of constraints of orbital symmetry, prompting efforts at an independent synthesis that included a study of REH2 activation (E = N, P, As). Oxidative addition of REH2 to 1 afforded (silox)3HTaEHR (2-NHR, R = H, Me, nBu, C6H4-p-X (X = H, Me, NMe2); 2-PHR

  N个激活2由（SILOX）3 TA（1，SILOX =吨卜3的SiO），得到（SILOX）3 Ta═N-N═Ta（SILOX）3（1 2 -N 2）不尽管Δ发生ģ ° CALD = -55.6千卡/摩尔，因为轨道对称性的约束，促使在一个独立的合成，其中包括的研究努力的REH 2活化（E = N，P，As）的。氧化加成REH的2至1，得到（SILOX）3 HTaEHR（2 -NHR，R = H，Me中，Ñ卜，C 6ħ 4 - p -X（X = H，Me中，NME 2）; 2 -PHR，R ＝ H，Ph；2 -AsHR，R = H，PH），其经历1,2--H 2在剔除，以形成（SILOX）3 Ta═NR（1 = NR; R = H，Me中，Ñ卜，C 6 H ^ 4 - p -X（X = H（X射线）中，Me，NME 2，CF 3）），（SILOX）3 Ta═PR（1 ═PR; R = H，PH），和（SILOX）3
• Synthesis of Tungsten Oxo Alkylidene Complexes
  作者：Dmitry V. Peryshkov、Richard R. Schrock

  DOI：10.1021/om3008579

  日期：2012.10.22

  toluene at 100 °C produced the known tungsten oxo alkylidene complex W(O)(CH-t-Bu)Cl2(PMe2Ph)2 (1a) in 45% isolated yield. The neophylidene analogue W(O)(CHCMe2Ph)Cl2(PMe2Ph)2 was prepared similarly in 39% yield. The reaction between 1a and LiOR (LiOR = LiOHIPT, LiOHMT) in benzene at 22 °C led to formation of the off-white W(O)(CH-t-Bu)Cl(OR)(PMe2Ph) complexes 4a (OR = OHMT = 2,6-dimesitylphenoxide)

  W（O）2（CH 2 - t- Bu）2（Bipy）与ZnCl 2（二恶烷），PMe 2 Ph和三甲基甲硅烷基氯的混合物在甲苯中于100°C反应生成已知的钨氧代亚烷基络合物W （O）（CH- t- Bu）Cl 2（PMe 2 Ph）2（1a），分离产率为45％。类似地以39％的收率制备了新叶绿素类似物W（O）（CHCMe 2 Ph）Cl 2（PMe 2 Ph）2。1a之间的反应和LIOR（LIOR = LiOHIPT，LiOHMT）的苯在22℃下导致形成灰白色W（O）（CH-的吨-Bu）氯（OR）（PME 2 PH）络合物4A（OR = OHMT = 2,6-二甲氧基苯酚）和4b（OR = OHIPT = 2,6-（2,4,6-三异丙基苯基）2苯氧基）。化合物4a用作合成W（O）（CH- t- Bu）（OHMT）（2,6-二苯基吡咯化物）（6），W（O）（CH- t- Bu）[N（ C 6
• Thermodynamics, Kinetics, and Mechanism of (silox)₃M(olefin) to (silox)₃M(alkylidene) Rearrangements (silox = ^tBu₃SiO; M = Nb, Ta)
  作者：Kurt F. Hirsekorn、Adam S. Veige、Michael P. Marshak、Yelena Koldobskaya、Peter T. Wolczanski、Thomas R. Cundari、Emil B. Lobkovsky

  DOI：10.1021/ja046180k

  日期：2005.4.1

  (silox)(3)M(ole) (silox = (t)Bu(3)SiO; M = Nb (1-ole), Ta (2-ole); ole = C(2)H(4), C(2)H(3)Me, C(2)H(3)Et, C(2)H(3)C(6)H(4)-p-X (X = OMe, H, CF(3)), C(2)H(3)(t)Bu, (c)C(5)H(8), (c)C(6)H(10), (c)C(7)H(10) (norbornene)) rearrange to alkylidene isomers (silox)(3)M(alk) (M = Nb (1=alk), Ta (2=alk); alk = CHMe, CHEt, CH(n)Pr, CHCH(2)C(6)H(4)-p-X (X = OMe, H, CF(3) (Ta only)), CHCH(2)(t)Bu, (c)C(5)H(8),

  烯烃配合物 (silox)(3)M(ole) (silox = (t)Bu(3)SiO; M = Nb (1-ole), Ta (2-ole); ole = C(2)H(4) , C(2)H(3)Me, C(2)H(3)Et, C(2)H(3)C(6)H(4)-pX (X = OMe, H, CF(3) ), C(2)H(3)(t)Bu, (c)C(5)H(8), (c)C(6)H(10), (c)C(7)H(10) (降冰片烯)) 重排为亚烷基异构体 (silox)(3)M(alk) (M = Nb (1=alk), Ta (2=alk); alk = CHMe, CHEt, CH(n)Pr, CHCH(2) )C(6)H(4)-pX (X = OMe, H, CF(3) (Ta only)), CHCH(2)(t)Bu, (c)C(5)H(8), ( c)C(6)H(10)、(c)C(
• Synthesis and Reactivity of [(silox)₂MoNR]₂Hg (R = ^tBu, ^tAmyl; silox = OSi^tBu₃):  Unusual Thermal Stability and Ready Nucleophilic Cleavage Rationalized by Electronic Factors
  作者：Devon C. Rosenfeld、Peter T. Wolczanski、Khaldoon A. Barakat、Corneliu Buda、Thomas R. Cundari、Frank C. Schroeder、Emil B. Lobkovsky

  DOI：10.1021/ic7010953

  日期：2007.11.1

  strong (L=PMe, pyridine, S8) or weak (L=2-butyne, ethylene, N2O, 1,4,7,10-tetrathiacyclododecane, 1,4,7,10,13,16-hexathiacyclooctadecane) nucleophiles, an enhanced rate of Mo-Hg bond cleavage was noted, with some of the former group generating adducts in <5 min; the products were 6-tBu, 7-py, (silox)2(S)Mo=NtBu (10-tBu), (silox)2Mo=NtBu(C2Me2) (8-tBu), (silox)2(C2H4)Mo=NtBu (11-tBu), (silox)2(O)Mo=NtBu

  （DME）Cl2Mo（= NR）2（R = tBu，（1-tBu），tAmyl（1-tAmyl））用2当量的tBu3SiOH（siloxH）和1当量的HCl处理产生的（silox）2Cl2Mo = NR（ R ＝ tBu，（3-tBu），t-戊基（3-tAmyl））；随后用Na / Hg还原得到Mo（V）氯化物（silox）2ClMo = NtBu（4-tBu）和Mo（IV）汞衍生物[[silox）2Mo = NR] 2Hg（R = tBu（（ 5-tBu）2 Hg），tAmyl（（5-tAmyl）2 Hg））。在L（L = PMe3，吡啶，4-甲基吡啶）存在下还原3-tBu和3-tAmyyl导致分离出加合物（silox）2（Me3P）Mo = NR（R = tBu（6-tBu） ，tAmyl（6-tAmyl））和（silox）2L2Mo = NtBu（L = py（7-py），4-pic
• Carbon monoxide cleavage by (silox)3Ta (silox = tert-Bu3SiO-): physical, theoretical, and mechanistic investigations
  作者：David R. Neithamer、Robert E. LaPointe、Ralph A. Wheeler、Darrin S. Richeson、Gregory D. Van Duyne、Peter T. Wolczanski

  DOI：10.1021/ja00207a011

  日期：1989.12

  (silox)sub 3}TaClsub 2} (1, silox = sup t}Busub 3}SiOsup minus}}) with Na/Hg in THF leads to a three-coordinate, Ta(III) siloxide, (silox)sub 3}Ta (2). Derivatization of 2 with excess Osub 2} or Hsub 2} provides (silox)sub 3}Ta = O (3) and (silox)sub 3}TaHsub 2} (4), respectively. At 25degree}C, carbonylation of 2 (0.1-1.0 atom) generates 1/2}sup 3} and 1/4}((silox)sub 3}Ta)sub 2}(mu}-Csub

  在 THF 中用 Na/Hg 还原 (silox)sub 3}TaClsub 2} (1, silox = sup t}Busub 3}SiOsup minus}}) 导致三坐标 Ta (III) siloxide，(silox)sub 3}Ta (2)。用过量的 Osub 2} 或 Hsub 2} 衍生 2 分别提供 (silox)sub 3}Ta = O (3) 和 (silox)sub 3}TaHsub 2} (4)。在 25°C，2（0.1-1.0 个原子）的羰基化生成 1/2}sup 3} 和 1/4}((silox)sub 3}Ta)sub 2}(mu} -Csub 2}) (5)，与 0.47 当量的 CO 吸收一致。二碳化物 5 的 X 射线 (Pbar 1}, R = 9.6%) 结构、IR 和拉曼研究表明近线性 mu}-Csub