tris(4-methylpyrazolyl)methane | 146175-64-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: tris(4-methylpyrazolyl)methane
• 英文别名: tris(4-methylpyrazolyl)methane C13H16N6, monoclinic；(4-Mepz)3CH；Tris(4-methyl-pyrazol-1-yl)methane；1-[bis(4-methylpyrazol-1-yl)methyl]-4-methylpyrazole
• CAS: 146175-64-6
• 化学式: C₁₃H₁₆N₆
• 分子量: 256.31
• InChiKey: LJMLUORSLCVPEE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  53.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tris(4-methylpyrazolyl)methane 、 copper(ll) bromide 以 甲醇 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Synthesis, spectroscopic and structural characterization of Cu(II) derivatives of tris(pyrazol-1-yl)methanes

  摘要：

  The reaction between CuX2 (X = ClO4, NO3, Cl, Br and CH3COO) and excess of tris(pyrazol-1-yl)methane ligands L (L = CH(pz)(3). CH(4-Mepz)(3), CH(3,5-Me(2)pz)(3), CH(3,4,5-Me(3)pz)(3) or CH(3-Mepz)(2)(5-Mepz)) yields [CuX2(L)], [{CuX2}(3)(L-2)(2)] or [Cu(L-2)]X-2-type complexes. The ligand to metal ratio is dependent on the number and disposition of the Me substituents on the azole-type ligand and mainly on the nature of the counter-ion X. All complexes have been characterized in the solid state as well as in solution (IR and UV spectra, and conductivity determinations). The solid-state structures of [Cu{(3,5-Me(2)pz)(3)CH}(2)](NO3)(2), [Cu{(3,5-Me(2)pz)(3)CH}(2)](ClO4)(2).0.5H(2)O, [Cu{(3,4,5-Me(3)pz)(3)CH}(2)](NO3)(2).H2O, [Cu{(4-Mepz)(3)CH}(2)]Br-2.3H(2)O have been determined by single crystal X-ray studies. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)00772-7
• 作为产物：
  描述：

  4-甲基吡唑 、 氯仿 在 四丁基溴化铵 、 sodium carbonate 作用下， 以 水 为溶剂， 生成 tris(4-methylpyrazolyl)methane
  参考文献：
  名称：

  Iron complexes of tris(pyrazolyl)ethane ligands methylated in the 3-, 4-, and 5-positions

  摘要：

  Four tris(pyrazolyl)ethane (tpe) ligands were synthesized from tris(pyrazolyl)methane (tpm) starting materials. The new tpe ligands differ only in the placement of methyl groups on the pyrazole rings. For each tpe ligand, the 2:1 complex with Fe(II) was readily synthesized and the structures were determined by X-ray crystallography and characterized more completely by Fe-57 Mossbauer spectroscopy, H-1 NMR, and UV-Vis spectroscopy. The complexes all contain Fe(II) in the low spin (LS) state at low temperatures, but differ in Fe-N bond lengths and spectroscopic parameters. Methyl groups in the 5-position of the pyrazoles of the tpe ligand close the bite of the ligand, strengthening the ligand field and shifting the visible absorbance band of the complex to higher energies. Methyls in the 4-position had almost no effect on the ligand, making the iron(II) complex almost indistinguishable from that of the parent tpe ligand. Methyl groups in the 3-position of the tpe ligand cause an opening of the bite of the ligand, which is evidenced by increased Fe-N bond lengths in the complex and a shift of the visible absorbance to lower energies. The complex with methyls in the 3-position also starts to display spin crossover behavior near room temperature, whereas the other tpe complexes do not. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2014.08.046

文献信息

• Investigations on the Steric Accessibility of the Carbanionic Moiety in Zwitterionic Magnesium Tris(pyrazolyl)methanide Complexes. Synthesis and Characterisation of Bi- and Tri­metallic Complexes
  作者：Jens Meyer、Istemi Kuzu、Sandra González-Gallardo、Frank Breher

  DOI：10.1002/zaac.201200405

  日期：2013.2

  trimetallic complexes [MgC(pz)3}2(AlEt3)2] (5), [MgC(pz)3}(AlEt3)C(3, 5-Me2pz)3}] (6), and [MgC(4-Mepz)3}2(AlEt3)2] (7). Based on NMR spectroscopic investigations, including an X-ray structural analysis on single crystals of 5, only the parent tris(pyrazolyl)methanide C(pz)3}– and the 4-methyl-substituted ligand scaffolds form C-bound adducts with the Lewis acid. By quantifying the steric bulk of

  HC(pz)3 和 HC(4-Mepz)3 与 MgBu2 和 MgN(SiMe3)2}2 的反应得到两性离子复合物 [MgC(pz)3}2] (2) 和 [MgC (4-Mepz)3}2] (4) 分别含有“游离”锥体碳负离子（pz = 吡唑基）。2的固态结构已经确定。2 和 4 的反应以及最近报道的均配和杂配复合物 [MgC(3, 5-Me2pz)3}2] (1) 和 [MgC(3, 5-Me2pz)3}C (pz)3}] (3) 用路易斯酸 AlEt3 提供双金属和三金属配合物 [MgC(pz)3}2(AlEt3)2] (5), [MgC(pz)3}( AlEt3)C(3, 5-Me2pz)3}] (6) 和 [MgC(4-Mepz)3}2(AlEt3)2] (7)。基于 NMR 光谱研究，包括对 5 单晶的 X 射线结构分析，只有母体三（吡唑基）甲烷 C(pz)3}–
• Structure, magnetism and photomagnetism of mixed-ligand tris(pyrazolyl)methane iron(ii) spin crossover compounds
  作者：Boujemaa Moubaraki、Ben A. Leita、Gregory J. Halder、Stuart R. Batten、Paul Jensen、Jonathan P. Smith、John D. Cashion、Cameron J. Kepert、Jean-François Létard、Keith S. Murray

  DOI：10.1039/b708773j

  日期：——

  effect upon the relative positions of the Fe(II) chelate molecules in polymorph 1b than in polymorph 1a; this is thought to drive the cooperativity differences observed in the magnetism of the polymorphs. Comparisons are also made between 1 to 4 and their homoleptic, parent [Fe(L)2] 2+ materials. The complexes were screened for the LIESST (light induced excited spin state trapping) effect by measurements

  一系列[Fe（（R-pz）3 CH）（（3,5-Me 2 pz）3 CH）]（BF 4）2类型的双齿三齿螯合物具有以下特征：三吡唑基甲烷 配体，其中R的变化为H（复合物1结晶为多晶型物1a和1b）和4-Me（2），R的变化为CH 2 OH脱离甲烷碳（3）。一种三（吡啶基）甲烷还描述了类似物（4）。这三（3,5-二甲基吡唑基）甲烷 共同配体（3,5--ME 2 PZ），和BF 4 -的抗衡离子，在整个恒定。这些Fe（II）d 6化合物的自旋交联性质已通过可变温度磁性，穆斯堡尔谱和晶体学方法进行了详细探讨。讨论了围绕Fe（II）中心的八面体对称，晶体溶剂化物分子（1.5 MeCN在2中和2 MeCN在3中）和超分子/晶体堆积对畸变的影响。在1的情况下，吡唑环发生细微的扭曲（随温度变化），这对Fe（II）螯合多态性1b中的分子而不是多态性1a中的; 据认为，这会导致在多晶型物的磁性中观察到的协同
• Silver derivatives of tris(pyrazol-1-yl)methanes. A silver(I) nitrate complex containing a tris(pyrazolyl)methane coordinated in a bridging mode
  作者：Augusto Cingolani、Effendy、Domenico Martini、Maura Pellei、Claudio Pettinari、Brian W. Skelton、Allan H. White

  DOI：10.1016/s0020-1693(01)00690-9

  日期：2002.1

  The reaction of AgX (X = ClO4, NO3 or SO3CH3) acceptors with excesses of tris(pyrazol-1-yl)methane ligands L (L = CH(pz)(3) CH(4-MePZ)(3), CH(3,5-Me(2)pz)(3), CH(3,4,5-Me(3)pz)(3) or CH(3-MePZ)(2)(5-Mepz)) yields 1:1 [AgX(L)], 2:1 [Ag(L)(2)]X or 3:2 [(AgX)2(L)31 complexes. The ligand to metal ratio in all complexes is dependent on the number and disposition of the Me substituents on the azole ring of the neutral ligand and on the nature of the Ag(l) acceptor. All complexes have been characterized in the solid state as well as in solution (medium- and far-IR, H-1 and C-13 NMR and conductivity determinations) and the solid-state structures of [Ag(NO3)pz)(3)CH}]((infinity/infinity)) and [Ag(3,5-Me(2)pz)(3)CH}(2)]NO3 determined by single crystal X-ray studies. (C) 2002 Elsevier Science B.V. All rights reserved.
• Byers, Peter K.; Canty, Allan J.; Honeyman, R. Thomas, Gazzetta Chimica Italiana, 1992, vol. 122, # 9, p. 341 - 344
  作者：Byers, Peter K.、Canty, Allan J.、Honeyman, R. Thomas、Claramunt, Rosa M.、Lopez, Concepcion、et al.

  DOI：——

  日期：——
• Synthesis, Spectroscopic, and X-ray Diffraction Structural Studies of Tin(IV) Derivatives with Tris(pyrazol-1-yl)methanes
  作者：C. Pettinari、M. Pellei、A. Cingolani、D. Martini、A. Drozdov、S. Troyanov、W. Panzeri、A. Mele

  DOI：10.1021/ic9906252

  日期：1999.12.1

  The reaction of RSnCl3 (R = Me, Ph, or Bu-n) and SnX4 accepters (X = Cl, Br, or I) with equimolar amounts of tris(pyrazol-1-yl)methane ligands L (L = HC(pz)(3), HC(4-Mepz)(3), HC(3,5-Me(2)pz)(3), HC(3,4,5-Me(3)pz)(3), or HC(3-Mepz)(2)(5-Mepz) yields ionic 1:1 [LSnRCl2}(+)][SnRCl4}(-)] or [LSnX3}(+)][SnX5}(-)] and 2:1 [LSnRCl2}(+)](2)[SnRCl5}(2-)] or [LSnX3)(+)](2)[SnX6}(2-)] complexes, depending strongly on the number and position of the Me groups on the azole ring of the neutral ligand. These complexes, stable in air, have been characterized in the solid state (LR, MS-FAB) as well as in solution (H-1- and Sn-119-NMR, conductivity, and molecular weight determinations). The crystal and molecular structure of [HC(4-Me(2)pz)(3)(SnBuCl2)-Bu-n}(+)](2)[(SnBuCl5)-Bu-n}(2-)], [HC(3,5-Me(2)pz)(3)SnMeCl2}(+)]-[MeSnCl4}(-)], and [HC(3,4,5-Me(3)pz)(3)SnBr3}(+)][SnBr5}(-)] was determined by X-ray crystallography. The structures of the cations are very similar, the Sn atom being in a strongly distorted octahedral environment with the Sn-N bonds in the range 2.22-2.33 Angstrom whereas in the anions the Sn atoms are five-coordinate (trigonal-bipyramidal) in [MeSnCl4](-) and [SnBr5](-) and six-coordinate (octahedral) in [(SnBuCl5)-Bu-n](2-).