bis(5-(trimethylsilyl)-1H-pyrazol-1-yl)methane | 152405-76-0

• 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: bis(5-(trimethylsilyl)-1H-pyrazol-1-yl)methane
• 英文别名: bis-(5-trimethylsilylpyrazol-1-yl)methane；Bis(5-trimethylsilylpyrazol-1-yl)methane；Trimethyl-[2-[(5-trimethylsilylpyrazol-1-yl)methyl]pyrazol-3-yl]silane
• CAS: 152405-76-0
• 化学式: C₁₃H₂₄N₄Si₂
• 分子量: 292.531
• InChiKey: XPFSHESMEIKGQI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.68
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  35.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  NbCl3(1,2-dimethoxyethane)(PhC.tplbond.CPh) 、 bis(5-(trimethylsilyl)-1H-pyrazol-1-yl)methane 以 二氯甲烷 为溶剂， 以85%的产率得到[NbCl3(bis(5-trimethylsilylpyrazol-1-yl)methane)(PhC.tplbond.CPh)]* 0.5 CH2Cl2
  参考文献：
  名称：

  Synthesis, spectroscopic characterization and dynamic behaviour of niobium complexes with poly(pyrazol-1-yl)methane ligands

  摘要：

  The complex [{NbCl3(dme)}(n)] 1 (dme = 1,2-dimethoxyethane) reacted with an excess of bis(pyrazol-1-yl)methane (bzpm), bis(3.5-dimethylpyrazol-1-yl)methane (bdmpzm) or bis(5-trimethylsilylpyrazol-1-yl)methane (btpzm) to give the binuclear complexes [{NbCl3(bpzm)}(2)] 2, [{NbCl3(bdmpzm)}(3)] 3 and [{NbCl3(btpzm)}(2)] 4, respectively. Mononuclear acetylene complexes [NbCl3(L-L)(RC drop CR')] (R = R' = Ph, L-L = bpzm 5, bdmpzm 6 or btpzm 7; R = R' = CO(2)Me, L-L = btpzm 8; R = R' = Me, L-L = bpzm 9, bdmpzm 10 or btpzm 11) have been prepared from either the reaction of 2-4 with acetylenes or the interaction of acetylene complexes [NbCl3(dme)(RC drop CR')] with the appropriate L-L. This last reaction with tris(pyrazol-1-yl)methane (tpzm) or tris(3,5-dimethylpyrazol-1-yl)methane (tdmpzm) in the presence of 1 equivalent of AgBF4 afforded the cationic complexes [NbCl2(L-L-L)(RC drop CR')]BF4 (R = R' = Ph, L-L-L = tpzm 12 or tdmpzm 13; R = R' = Me, L-L-L = tpzm 14 or tdmpzm 15). The structures of these complexes have been determined by spectroscopic methods. Variable-temperature NMR studies of some of the complexes were carried out in order to establish their fluxional behaviour in solution and free activation energy values were calculated at the coalescence temperature.

  DOI：

  10.1039/dt9950001015
• 作为产物：
  描述：

  三甲基氯硅烷 、 1-(1-吡唑甲基)吡唑 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以85%的产率得到bis(5-(trimethylsilyl)-1H-pyrazol-1-yl)methane
  参考文献：
  名称：

  Formation of dilithiated bis-(1H-pyrazol-1-yl)alkanes and their application in the synthesis of diboronic acids

  摘要：

  Bis-(1H-pyrazol-1-yl)alkanes were deprotonated at the pyrazole 5-positions on treatment with LDA in THF at low temperature. These dianions reacted with tert-butylisocyanate as the electrophile to install a tert-butylamide group at the pyrazole 5-position. The obtained amides were next converted into the respective diboronic acids by Br-Li exchange with t-BuLi in THF at low temperature, followed by the use of triethyl borate as the electrophile. The X-ray analysis of the obtained diboronic acids revealed the presence of a variety of structural motifs, which stabilize the structure by hydrogen bond formation. The stabilization pattern differs greatly with a minor modification of the linker connecting the pyrazole rings. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.01.007

文献信息

• Synthesis and spectroscopic studies of ruthenium complexes with poly(pyrazol-1-yl) methane ligands. Crystal structure of [RuCl(cod)(tpzm)]Cl·EtOH [cod = cycloocta-1,5-diene, tpzm = tris(pyrazol-1-yl)methane]
  作者：Mariano Fajardo、Antonio de la Hoz、Enrique Diéz-Barra、Félix A. Jalón、Antonio Otero、Ana Rodríguez、Juan Tejeda、Daniele Belletti、Maurizio Lanfranchi、Maria Angela Pellinghelli

  DOI：10.1039/dt9930001935

  日期：——

  Neutral six-co-ordinate complexes of RuII, [RuCl2(btpzm)(cod)]1 and [RuCl2(btpzm)(cod)]2 with bis(pyrazol-1-yl)methane (bpzm) or bis (5-trimethylsilylpyrazol-1-yl)methane (btpzm) were synthesised from [RuC2(cod)}n](cod = cycloocta-1,5-diene) and the corresponding ligand. Complex 1 reacts with LiBEt3H to give the hydride [RuH(Cl)(bpzm)(cod)]3. The reactitivity of 2 allowed the synthesis of the new

  Ru II，[RuCl 2（btpzm）（cod）] 1和[RuCl 2（btpzm）（cod）] 2与双（吡唑-1-基）甲烷（bpzm）或bis（由[RuC 2（cod）} n ]（cod =环辛基-1,5-二烯）和相应的配体合成5-三甲基甲硅烷基吡唑-1-基）甲烷（btpzm）。配合物1与LiBEt 3 H反应生成氢化物[RuH（Cl）（bpzm）（cod）] 3。的reactitivity 2所允许的新络合物的合成将[RuCl 2（btpzm）2 ]·0.5thf 4（thf =四氢呋喃）具有两个双齿btpzm配体。[RuCl 2（cod）} n ]与三（吡唑-1-基）甲烷配体（tpzm）的反应生成六坐标阳离子络合物[RuCl（cod）（tpzm）] Cl·-EtOH 5。最后，[RuCl 3（tpzm）]与吡啶和三乙胺的反应得到[RuCl 2（py）（tpzm）] 6。提供了所
• Diez-Barra, Enrique; Hoz, Antonio de la; Sanchez-Migallon, Ana, Journal of the Chemical Society. Perkin transactions I, 1993, # 9, p. 1079 - 1084
  作者：Diez-Barra, Enrique、Hoz, Antonio de la、Sanchez-Migallon, Ana、Tejeda, Juan

  DOI：——

  日期：——
• Formation of dilithiated bis-(1H-pyrazol-1-yl)alkanes and their application in the synthesis of diboronic acids
  作者：Krzysztof Durka、Agnieszka Górska、Tomasz Kliś、Janusz Serwatowski、Krzysztof Woźniak

  DOI：10.1016/j.tetlet.2014.01.007

  日期：2014.2

  Bis-(1H-pyrazol-1-yl)alkanes were deprotonated at the pyrazole 5-positions on treatment with LDA in THF at low temperature. These dianions reacted with tert-butylisocyanate as the electrophile to install a tert-butylamide group at the pyrazole 5-position. The obtained amides were next converted into the respective diboronic acids by Br-Li exchange with t-BuLi in THF at low temperature, followed by the use of triethyl borate as the electrophile. The X-ray analysis of the obtained diboronic acids revealed the presence of a variety of structural motifs, which stabilize the structure by hydrogen bond formation. The stabilization pattern differs greatly with a minor modification of the linker connecting the pyrazole rings. (C) 2014 Elsevier Ltd. All rights reserved.
• Synthesis, spectroscopic characterization and dynamic behaviour of niobium complexes with poly(pyrazol-1-yl)methane ligands
  作者：Juan Fernández-Baeza、Félix A. Jalón、Antonio Otero、M. Esther Rodrigo-Blanco

  DOI：10.1039/dt9950001015

  日期：——

  The complex [NbCl3(dme)}(n)] 1 (dme = 1,2-dimethoxyethane) reacted with an excess of bis(pyrazol-1-yl)methane (bzpm), bis(3.5-dimethylpyrazol-1-yl)methane (bdmpzm) or bis(5-trimethylsilylpyrazol-1-yl)methane (btpzm) to give the binuclear complexes [NbCl3(bpzm)}(2)] 2, [NbCl3(bdmpzm)}(3)] 3 and [NbCl3(btpzm)}(2)] 4, respectively. Mononuclear acetylene complexes [NbCl3(L-L)(RC drop CR')] (R = R' = Ph, L-L = bpzm 5, bdmpzm 6 or btpzm 7; R = R' = CO(2)Me, L-L = btpzm 8; R = R' = Me, L-L = bpzm 9, bdmpzm 10 or btpzm 11) have been prepared from either the reaction of 2-4 with acetylenes or the interaction of acetylene complexes [NbCl3(dme)(RC drop CR')] with the appropriate L-L. This last reaction with tris(pyrazol-1-yl)methane (tpzm) or tris(3,5-dimethylpyrazol-1-yl)methane (tdmpzm) in the presence of 1 equivalent of AgBF4 afforded the cationic complexes [NbCl2(L-L-L)(RC drop CR')]BF4 (R = R' = Ph, L-L-L = tpzm 12 or tdmpzm 13; R = R' = Me, L-L-L = tpzm 14 or tdmpzm 15). The structures of these complexes have been determined by spectroscopic methods. Variable-temperature NMR studies of some of the complexes were carried out in order to establish their fluxional behaviour in solution and free activation energy values were calculated at the coalescence temperature.