((t-Bu)3SiO)3TaD2 | 1242420-70-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((t-Bu)3SiO)3TaD2
• 英文别名: ((t)Bu3SiO)3TaD2
• CAS: 1242420-70-7
• 化学式: C₃₆H₈₃O₃Si₃Ta
• 分子量: 831.242
• InChiKey: IILRPNMTIZNBHX-REZQDPELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.9
• 重原子数：
  43.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ((t-Bu)3SiO)3TaD2 在 CO 作用下， 生成
  参考文献：
  名称：

  Miller, Rebecca L.; Toreki, Robert; LaPointe, Robert E., Journal of the American Chemical Society, 1993, vol. 115, # 13, p. 5570 - 5588

  摘要：

  DOI：
• 作为产物：
  描述：

  (silox)3TaH2 、 氘 以 氘代苯 为溶剂， 生成 ((t-Bu)3SiO)3TaD2 、
  参考文献：
  名称：

  Miller, Rebecca L.; Toreki, Robert; LaPointe, Robert E., Journal of the American Chemical Society, 1993, vol. 115, # 13, p. 5570 - 5588

  摘要：

  DOI：

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
• Silox hydrides [silox = (Me3C)3SiO-] of Group 5: Do [(Me3C)3SiO]2MH2]2 (M = Nb, Ta) contain unbridged M-M bonds?
  作者：Robert E. LaPointe、Peter T. Wolczanski

  DOI：10.1021/ja00272a074

  日期：1986.6

  Complexes containing M-H bonds are widely recognized as being important intermediates in numerous catalytic processes. Investigations of early metal hydride reactivity have resulted in reagents useful in organic synthesis and modeling studies relevant to the Fischer-Tropsch process. A variety of group 5 hydrides have been described; the majority contain ancillary phosphine and/or cyclopentadienyl ligands

  含有 MH 键的配合物被广泛认为是许多催化过程中的重要中间体。对早期金属氢化物反应性的研究产生了可用于有机合成和与费托过程相关的建模研究的试剂。已经描述了多种第 5 族氢化物；大多数含有辅助膦和/或环戊二烯基配体，这些配体倾向于电子和空间饱和早期金属中心。通过引入具有与上述强σ供体不同的电子特性的辅助配体系统，可以改变这些金属氢化物共有的反应性和结构特性。本文报道了由三叔丁基硅氧化物 (t-Bu/sub 3/SiO/sup -/, silox) 连接的第 5 族氢化物的合成和选定反应，
• Insertion of H₂CCHX (X = F, Cl, Br, OⁱPr) into (^tBu₃SiO)₃TaH₂ and β-X-Elimination from (^tBu₃SiO)₃HTaCH₂CH₂X (X = OR):  Relevance to Ziegler−Natta Copolymerizations
  作者：Stephanie A. Strazisar、Peter T. Wolczanski

  DOI：10.1021/ja003315n

  日期：2001.5.1

  The insertion of H2C=CHX (X = OR; R = Me, Et, Pr-n,Pr-1, CH=CH2, Ph) into ((Bu3SiO)-Bu-t)(3)TaH2 (1) afforded ((Bu3SiO)-Bu-t)(3)HTaCH2CH2X (2-CH2CH2X), which beta -X-eliminated to give ethylene and ((Bu3SiO)-Bu-t)(3)- HTaX (3-X). beta -X-elimination rates were inversely proportional to the size of R. An X-ray crystallographic study of ((Bu3SiO)-Bu-t)(3)(HTaCH2CH2OBu)-Bu-t (2-(CH2CH2OBu)-Bu-t) revealed a distorted trigonal bipyramidal structure with an equatorial plane containing be hydride and a -(CH2CH2OBu)-Bu-t ligand with a staggered disposition. erythro and threo-((Bu3SiO)-Bu-t)(3)HTaCHDCHDOEt (2-CHDCHDOEt) are staggered in solution, according to H-1 NMR spectroscopic studies, and eliminated cis- and trans-HDC=CHD, respectively, helping verify the four-centered transition state for beta -OEt-elimination. When X = F, Cl, or Br, 2-CH2CH2X was not observed en route to 3-X, signifying that olefin insertion was rate-determining. Insertion rates suggested that substantial positive charge on the substituted carbon was incurred. The reactivity of other H2C=CHX with 1, and a discussion of the observations and their ramifications on the incorporation of functionalized monomers in Ziegler-Natta copolymerizations, are presented.