1,1,1-tris(2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl)amine-d36 | 960157-60-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,1,1-tris(2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl)amine-d36
• 英文别名: TMG3tren-d36；2-[2-[Bis[2-[bis[bis(trideuteriomethyl)amino]methylideneamino]ethyl]amino]ethyl]-1,1,3,3-tetrakis(trideuteriomethyl)guanidine
• CAS: 960157-60-2
• 化学式: C₂₁H₄₈N₁₀
• 分子量: 476.393
• InChiKey: GMRXONOPMFULHG-MCDHJEQXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  31
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  59.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1,1-tris(2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl)amine-d36 、 iron(II) trifluoromethanesulfonate acetonitrile disolvate 以 四氢呋喃 为溶剂， 以91%的产率得到[Fe(II)(CH3CN)(TMG3tren-d36)](OTf)2
  参考文献：
  名称：

  高自旋氧化铁 (IV) 配合物的晶体结构及其自衰变途径的表征

  摘要：

  [Fe(IV)(O)(TMG(3)tren)](2+) (1; TMG(3)tren = 1,1,1-tris{2-[N(2)-(1,1, 3,3-四甲基胍基）]乙基}胺）是可分离的合成 S = 2 oxoiron (IV) 复合物的一个独特例子，可作为在非血红素铁酶中观察到的高价 oxoiron (IV) 中间体的模型。与预测更具反应性的 S = 2 氧化铁 (IV) 中心的 DFT 计算一致，1 的寿命明显短于相关 S = 1 氧化铁 (IV) 配合物的寿命。1 的自衰变表现出严格的一级动力学行为，不受溶剂氘化的影响，表明是分子内过程。这一假设得到了铁产品的 ESI-MS 分析和使用全氘甲基 TMG(3)tren 同位素 d(36)-1（KIE = 24 在 25 摄氏度）后显着延迟自衰变的支持。d(36)-1 大大增强的热稳定性允许获得高分辨率晶体结构的衍射质量晶体的生长。这种结构在由四齿三足

  DOI：

  10.1021/ja100366c

文献信息

• Isotopic Probing of Molecular Oxygen Activation at Copper(I) Sites
  作者：Michael P. Lanci、Valeriy V. Smirnov、Christopher J. Cramer、Ekaterina V. Gauchenova、Jörg Sundermeyer、Justine P. Roth

  DOI：10.1021/ja074620c

  日期：2007.11.28

  Copper-dioxygen (CUO2) adducts are frequently proposed as intermediates in enzymes, yet their electronic and vibrational structures have not always been understood. [Cu(eta(1)-O-2)TMG(3)tren](+) (TMG(3)-tren = 1,1,1-tris2-[N-2-(1,1,3,3-tetramethylguanidino)]ethyl}amine) features end-on (eta(1)) O-2 coordination in the solid state. Described here is an investigation of the compound's solution properties by nuclear magnetic resonance spectroscopy, density functional calculations, and oxygen isotope effects. The study yields two major findings. First, [CU(eta(1)-O-2)TMG(3)tren](+) is paramagnetic due to a triplet electronic structure; this is in contrast to other copper compounds where O-2 is bound in a side-on manner. Second, the oxygen equilibrium isotope effect upon O-2 binding to copper(I) (O-18 EIE equivalent to K((OO)-O-16-O-16)IK((OO)-O-16-O-18) = 1.0148 +/- 0.0012) is significantly larger than those determined for iron and cobalt eta(1)-O-2 adducts. This result is suggested to reflect greater ionic (Cu-II-O-2(-1)) character within the valence bond description. A revised interpretation of the physical origins of the O-18 ElEs upon O-2 binding to redox metals is also advanced along with experimental data that should be used as benchmarks for interpreting O-18 kinetic isotope effects upon enzyme reactions.