N-benzylbis(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)amine | 167224-34-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-benzylbis(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)amine
• 英文别名: benzylbis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine；bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]benzylamine；benzyl-bis[2-(3,5-dimethylpyrazolyl)ethyl]amine；N-benzyl-2-(3,5-dimethylpyrazol-1-yl)-N-[2-(3,5-dimethylpyrazol-1-yl)ethyl]ethanamine
• CAS: 167224-34-2
• 化学式: C₂₁H₂₉N₅
• 分子量: 351.495
• InChiKey: QTIZTTDQMMRWOJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  38.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  copper(II) perchlorate hexahydrate 、 N-benzylbis(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)amine 以 乙醇 为溶剂， 生成 [Cu(benzylbis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine)(EtOH)(H2O)(2+)](ClO4)2*[Cu(benzylbis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine)(EtOH)(ClO4)]ClO4
  参考文献：
  名称：

  X-ray Structures and Redox Properties of Copper(II) Bis(pyrazole) Complexes

  摘要：

  The copper complexes of bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl] amine (1) and its benzylated derivative (2) have been studied as single crystals by X-ray crystallography and as powders and solutions by a variety of techniques. [Cu(1). 2NO(3)] (C14H25CuN7O7 including 1 H2O, 3) crystallized in the monoclinic space group Pc (No. 7) with a = 8.1596(9) Angstrom, b = 31.164(2) Angstrom, c = 7.7966(9) Angstrom, beta = 94.75(2)degrees, V = 1975.7(3) Angstrom(3), and Z = 4 (structure refinement converged to R(F) = 0.066 and R(wF)(2) = 0.227); [Cu(1)ClO4 . C2H5OH]ClO4 (C16H29Cl2CuN5O9, 4) crystallized in the orthorhombic space group Pna2(1) (No. 33) with a = 13.3463(7) Angstrom, b = 10.3925(9) Angstrom, c = 17.511(1) Angstrom, V = 2432.1(3) Angstrom(3), and Z = 4 (refined to R(F) = 0.063 and R(wF) = 0.052); [Cu(2). 2NO(3)] (C21H29CuN7O6, 5) crystallized in the monoclinic space group C2/c (No. 15) with a = 28.719(2) Angstrom, b = 8.6043(6) Angstrom, c = 23.034(2) Angstrom, beta = 124.767(7)degrees, V = 4675.7(7) Angstrom(3), and Z = 8 (refined to R(F) = 0.042 and R(wF) = 0.034); [Cu .(2). C2H5OH . Y](ClO4)(n) (C48H78Cl4Cu2N10O20, 6) (Y = H2O, n = 2, or ClO4-, n = 1) crystallized in the monoclinic space group P2(1)/c (No. 14) with a = 10.9488(9) Angstrom, b = 17.030(2) Angstrom, c = 32.893(3) Angstrom, beta = 92.185(7)degrees, V = 6129(1) Angstrom(3) and Z = 4 (refined to R(F) = 0.104 and R(wF) = 0.119). In complexes 3, 4, and 6, the ligand coordinated Cu(II) with a T-shaped arrangement of the nitrogen donor atoms. Ethanol coordinated in one of the apical positions in complexes 4 and 6. The amine nitrogen moved from the basal plane in 3 to the apical position in 5, where the copper had square pyramidal coordination geometry. The largest difference between 4 and 6 was a lengthening of 0.1 Angstrom in the bond between the Cu(II) and the amine nitrogen. Conductivity measurements revealed that the nitrate complexes behave as 1:1 electrolytes in acetonitrile solution, whereas the perchlorate complexes behaved as 2:1 electrolytes. The half-wave potentials, measured in acetonitrile by cyclic voltammetry, were -0.01, +0.15, +0.10, and +0.28 V for 3-6, respectively. The high redox potentials of the copper(II) bis(pyrazole) complexes, in particular for complex 6, are explained by the fact that the Cu(II) complexes have the correct ligand geometry for the stabilization of Cu(I).

  DOI：

  10.1021/ic00123a005

文献信息

• Highly efficient palladium precatalysts of homoscorpionate bispyrazolyl ligands for the more challenging Suzuki–Miyaura cross-coupling of aryl chlorides
  作者：Alex John、Mobin M. Shaikh、Ray J. Butcher、Prasenjit Ghosh

  DOI：10.1039/c003174g

  日期：——

  Highly efficient palladium precatalysts [RN-(CH2)n-pz3,5-Me2}2]PdCl2}m [m = n = 1; R = 2,6-Me2C6H3 (1), 2,4,6-Me3C6H2 (2), CH2Ph (3) and m = n = 2; R = CH2Ph (4)] of a series of homoscorpionate bispyrazolyl ligands for the Suzuki–Miyaura cross-coupling of the more challenging aryl chloride substrates are reported. In particular, the palladium 1–4 precatalysts carried out the Suzuki–Miyaura cross-coupling

  高效率 钯预催化剂[RN -（CH 2）n -pz 3,5-Me 2 } 2 ] PdCl 2 } m [ m = n = 1；R = 2,6-Me 2 C 6 H 3（1），2,4,6-Me 3 C 6 H 2（2），CH 2 Ph（3）和m = n = 2; R = CH 2 Ph（4）]双吡唑基据报道，具有挑战性的芳基氯化物底物的Suzuki-Miyaura交叉偶联的配体。特别是，钯1-4预催化剂对具有吸电子，给电子和杂芳基取代基的多种芳基氯化物底物进行了Suzuki-Miyaura交叉偶联。足够明显的是，通过X射线衍射研究确定了1-4种预催化剂的分子结构，发现在亚甲基桥联的单核1-3种配合物中存在反电[C–H⋯Pd]型相互作用。双吡唑基 配体，而 乙烯桥接类似物4产生了有趣的二聚体20元大环金属配合物，没有任何这种相互作用。
• Chromium Catalysts Based on Tridentate Pyrazolyl Ligands for Ethylene Oligomerization
  作者：Fernando Junges、Maria C. A. Kuhn、Ana H. D. P dos Santos、Carlos R. K. Rabello、Christophe M. Thomas、Jean-François Carpentier、Osvaldo L. Casagrande

  DOI：10.1021/om070215i

  日期：2007.7.30

  A set of chromium(III) complexes CrCl3(L) based on tridentate ligands (1, L = bis[2-(3,5-dimethylpyrazolyl)ethyl)]amine; 2, L = bis[2-(3,5-dimethyl-l-pyrazolyl)ethyl]benzylamine; 3, L = bis[2-(3,5-dimethyl-l-pyrazolyl)ethyl] ether; 4, L = bis[2-(3-phenyl-l-pyrazolyl)ethyl] ether; 5, L = bis[2-(3,5-dimethyl-l-pyrazolyl)ethyl] sulfide)) have been prepared and characterized by elemental analysis, ESI-HRMS

  一组基于三齿配体（1，L =双[2-（3,5-二甲基吡唑基）乙基]胺的铬（III）络合物CrCl 3（L）；2，L ＝双[2-（3，5-二甲基-1-吡唑基）乙基]苄胺；3，L ＝双[2-（3，5-二甲基-1-吡唑基）乙基]醚；4，L ＝双[2-（3-苯基-1-吡唑基）乙基]醚；5，L =双[2-（3,5-二甲基-1-吡唑基）乙基]硫醚））已经被制备和表征通过元素分析，ESI-HRMS，和用于X射线衍射研究3。经甲基铝氧烷（MAO）活化后，这些预催化剂在乙烯低聚反应中显示出高活性（TOF =（3.4-131.0）×10 3（mol乙烯）（mol Cr）-1 h在80°C时为-1），选择性地生产出C 4 -C 14+范围内的α-烯烃。催化性能基本上受配体环境，特别是桥供体原子和反应条件的影响。在优化的条件下（[Cr] = 10μmol，80°C，乙烯40 bar，MAO-Cr = 300），预催化剂5的TOF
• Five-coordinate metal(II) complexes based pyrazolyl ligands
  作者：Salah S. Massoud、Febee R. Louka、Regan N. David、Merlin J. Dartez、Quang L. Nguyn、Nicholas J. Labry、Roland C. Fischer、Franz A. Mautner

  DOI：10.1016/j.poly.2015.02.014

  日期：2015.4

  The reactions of pyrazole based ligands with M(II) perchlorate hexahydrate in the presence of NH4NCS afforded the mononuclear complexes [Co(Bzbedmpza)(NCS)(2)]center dot 3/4CH(3)COCH(3) (1), [Ni(Bzbedmpza)(NCS)(2)] (2), [Cu(Bzbedmpza)(NCS)(2)] (3) and [Cu(Mebedmpza)(NCS)(2)] (4), and in the presence of NaN3, the complex [Cu(tedmpza)(N-3)]ClO4 (5) was isolated where Bzbedmpza = N-benzyl-bis(3,5-dimethyl-2-(pyrazol-1H-yl)ethyl)amine, Mebedmpza = N-methyl-bis(3,5-dimethyl-2-(pyrazol-1H-yl)ethyl)amine and tedmpza = tris(2,5-dimethyl-ethyl-pyrazol-1H-yl)amine. The complexes were structurally characterized by elemental microanalyses, IR and UV-Vis spectroscopy and by single crystal X-ray crystallography. The complexes 2-5 display distorted SP geometry, whereas the cobalt(II) complex 1 has a distorted TBP. Also, all the thiocyanato complexes 1-4 are coordinated to the central metal ions through N-terminal thiocyanate. The stability of any of the two possible limiting geometries (SP versus TBP) including nature of the central metal ion and the structural parameters of the amine coligands (steric effect, nature of chelate ring sizes and skeleton of the coligand) are analyzed as a function tau values. (C) 2015 Elsevier Ltd. All rights reserved.