tris((N-tert-butylcarbamoyl)methyl)amine | 168646-40-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tris((N-tert-butylcarbamoyl)methyl)amine
• 英文别名: tris(N-tert-butylcarbamoylmethyl)amine；2-[bis[2-(tert-butylamino)-2-oxoethyl]amino]-N-tert-butylacetamide
• CAS: 168646-40-0
• 化学式: C₁₈H₃₆N₄O₃
• 分子量: 356.509
• InChiKey: LLGLWGDQIZSIPI-UHFFFAOYSA-N

物化性质

• 沸点：
  585.8±45.0 °C(Predicted)
• 密度：
  1.016±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  25
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  90.5
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tris((N-tert-butylcarbamoyl)methyl)amine 以 N,N-二甲基甲酰胺 为溶剂， 生成 tetraethylammonium [tris((N-tert-butylcarbamoyl)methyl)aminato]zincate(II)
  参考文献：
  名称：

  Structure and Physical Properties of Trigonal Monopyramidal Iron(II), Cobalt(II), Nickel(II), and Zinc(II) Complexes

  摘要：

  A series of trigonal monopyramidal complexes of the tripodal ligand tris((N-rert-butylcarbamoyl)methyl)aminato, [1(But)](3-), have been synthesized and characterized. The structures of [Co1(But)](-), [Zn1(But)](-), and [Ni1(But)](-) confirm that trigonal monopyramidal coordination geometry occurs in these complexes where the three amidate nitrogens are arranged in the trigonal plane and the amine nitrogen is bonded apically to the metal ions. The solid-state structures of [Co1(But)](-), [Zn1(But)](-), and [Ni1(But)](-) are nearly identical indicating that the trigonal ligand [1(But)](3-) enforces the trigonal monopyramidal structure in these metal ions. Crystal data: K[Co1(But)].0.5DMF crystallizes in the monoclinic space group C2/c, with cell dimensions a = 18.844(4) Angstrom, b = 9.809(3) Angstrom, c = 28.715(13) Angstrom, beta = 102.70 degrees, and Z = 8; (NEt4)[Zn1(But)].THF crystallizes in the monoclinic space group P2(1)/c, with cell dimensions a = 13.244(3) Angstrom, b = 11.285(5) Angstrom, c = 25.625(3) Angstrom, beta = 104.45(1)degrees and Z = 4. The H-1 NMR spectrum of the diamagnetic [Zn1(But)](-) also suggests that the complex retains its C-3 symmetry in solution. Room-temperature magnetic susceptibility measurements show that [Fe1(But)](-), [Co1(But)](-), and [Ni1(But)](-) are high spin. The cyclic voltammetry of [Co1(But)](-) and [Ni1(But)](-) at a glassy carbon surface and at a scan rate of 100 mV s(-1) shows quasi-reversible one electron oxidation at E-1/2 = 0.77 (Delta E-p = 93 mV, i(pc)i(pa)(-1) = 0.69) and 0.56 (Delta E-p = 75 mV, i(pc)i(pa)(-1) = 0.79) V versus SCE, respectively. However, at slower scan rates these redox processes become irreversible and attempts to isolate the oxidized products at room temperature were unsuccessful. The chemical oxidation of [Ni1(But)](-) with [Fe(bpy)(3)](3-) in 1:1 propionitrile-DMF mixture at -75 degrees C generated a EPR-active species (77 K, g(1) = 2.29, g(2) = 2.16, g(3) = 2.03, a(3) = 20 G) assigned to a Ni(III) complex with rhombic symmetry. [Fe1(But)](-) shows one irreversible oxidation (E-p,E-a = 0.05 V versus SCE) under the same conditions. These results are consistent with [1(But)](3-) being able to stabilize trigonal monopyramidal complexes of low-valent metal ions.

  DOI：

  10.1021/ic970831e
• 作为产物：
  描述：

  次氮基三乙酸 、 叔丁胺 在 吡啶 、 亚磷酸三苯酯 作用下， 反应 20.0h， 以35%的产率得到tris((N-tert-butylcarbamoyl)methyl)amine
  参考文献：
  名称：

  Mononuclear Single-Molecule Magnets: Tailoring the Magnetic Anisotropy of First-Row Transition-Metal Complexes

  摘要：

  Magnetic anisotropy is the property that confers to the spin a preferred direction that could be not aligned with an external magnetic field. Molecules that exhibit a high degree of magnetic anisotropy can behave as individual nanomagnets in the absence of a magnetic field, due to their predisposition to maintain their inherent spin direction. Until now, it has proved very hard to predict magnetic anisotropy, and as a consequence, most synthetic work has been based on serendipitous processes in the search for large magnetic anisotropy systems. The present work shows how the property can be predicted based on the coordination numbers and electronic structures of paramagnetic centers. Using these indicators, two Co-II complexes known from literature have been magnetically characterized and confirm the predicted single-molecule magnet behavior.

  DOI：

  10.1021/ja4015138

文献信息

• Synthesis and characterization of a trigonal monopyramidal nickel(II) complex
  作者：Manabendra Ray、Glenn P. A. Yap、Arnold L. Rheingold、A. S. Borovik

  DOI：10.1039/c39950001777

  日期：——

  An unusual trigonal monopyramidal nickel(II) complex of a new tripodal tris-(N-tert-butylcarbamoylmethyl)aminato (3–) ligand is reported; this ligand sterically protects the NiII centre preventing further ligand coordination.

  一个不寻常的三角monopyramidal镍（II）复合物的新的三足三- （的ñ -叔-butylcarbamoylmethyl）aminato（3-）配体被报告; 该配体在空间上保护Ni II中心，防止进一步的配体配位。
• Huge Magnetic Anisotropy in a Trigonal-Pyramidal Nickel(II) Complex
  作者：Silvia Gómez-Coca、Eduard Cremades、Núria Aliaga-Alcalde、Eliseo Ruiz

  DOI：10.1021/ic402256v

  日期：2014.1.21

  The work presented herein shows the experimental and theoretical studies of a mononuclear nickel(II) complex with the largest magnetic anisotropy ever reported. The zero-field-splitting D parameter, extracted from the fits of the magnetization and susceptibility measurements, shows a large value of -200 cm(-1), in agreement with the theoretical value of -244 cm(-1) obtained with the CASPT2-RASSI method.