3,3,9,9-tetraethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene | 899838-79-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 3,3,9,9-tetraethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene
• 英文别名: 3,3,7,7-tetraethyl-4,6,8,9-tetrahydro-2H-pyrimido[1,2-a]pyrimidine
• CAS: 899838-79-0
• 化学式: C₁₅H₂₉N₃
• 分子量: 251.415
• InChiKey: FAMPOZJHHBFUMZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  27.6
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,3,9,9-tetraethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene 在 盐酸 作用下， 以 邻二氯苯 为溶剂， 反应 1.0h， 以100%的产率得到3,3,9,9-tetraethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene hydrochloride
  参考文献：
  名称：

  Syntheses of very soluble alkylated bicyclic guanidinate ligands and structural characterization of a dipalladium paddlewheel

  摘要：

  Fool-proof syntheses of two highly soluble tetraalkylated bicyclic guanidinates which are characterized by the NC(N)N core are reported along with the structures of the corresponding hydrochlorides. The compound with alkyl = methyl was used to prepare a paddlewheel species with a Pd-2(4+) core devoid of a strong metal-metal bond but potentially useful as precursor to a rare single bonded Pd-2(6+) species. The Pd1...Pd2 separation is only 2.5488(12) angstrom and the local coordination for each of the d(8) Pd(II) atoms is square planar. Published by Elsevier Ltd.

  DOI：

  10.1016/j.poly.2012.06.002
• 作为产物：
  描述：

  N,N-bis(2,2-diethyl-3-iminohydroxypropyl)amine hydrochloride 在 二硫化碳 、 对甲苯磺酸 、 sodium hydroxide 作用下， 以 乙醇 、 对二甲苯 、 水 为溶剂， 100.0 ℃ 、7.58 MPa 条件下， 反应 76.0h， 生成 3,3,9,9-tetraethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene
  参考文献：
  名称：

  Syntheses of very soluble alkylated bicyclic guanidinate ligands and structural characterization of a dipalladium paddlewheel

  摘要：

  Fool-proof syntheses of two highly soluble tetraalkylated bicyclic guanidinates which are characterized by the NC(N)N core are reported along with the structures of the corresponding hydrochlorides. The compound with alkyl = methyl was used to prepare a paddlewheel species with a Pd-2(4+) core devoid of a strong metal-metal bond but potentially useful as precursor to a rare single bonded Pd-2(6+) species. The Pd1...Pd2 separation is only 2.5488(12) angstrom and the local coordination for each of the d(8) Pd(II) atoms is square planar. Published by Elsevier Ltd.

  DOI：

  10.1016/j.poly.2012.06.002

文献信息

• Weak acids with super-electron-donor dimetal complexes: Synergy in bifunctional activity
  作者：Matthew E. Humphries、Emily S. Wusterbarth、Dennis L. Lichtenberger

  DOI：10.1016/j.poly.2018.11.001

  日期：2019.1

  Abstract Dimetal paddlewheel complexes with bicyclic guanidine ligands are extremely strong thermodynamic electron donors. As a probe of the chemical potential and sites for chemical reactivity of these complexes, the interaction of Mo2(TEhpp)4 with weak acids was investigated (TEhpp is the anion of the bicyclic guanidine 3,3,9,9-tetraethyl-1,5,7-triazabicyclo[4.4.0.]dec-4-ene). Mo2(TEhpp)4 is readily

  摘要具有双环胍配体的双金属桨叶配合物是非常强的热力学电子供体。作为这些配合物的化学势和化学反应位点的探针，研究了Mo2（TEhpp）4与弱酸的相互作用（TEhpp是双环胍3,3,9,9-tetraethyl-1的阴离子， 5,7-三氮杂双环[4.4.0。] dec-4-ene）。Mo2（TEhpp）4很容易像预期的那样被乙酸和三氟乙酸质子化，但是出人意料的是，其机理比简单的酸碱质子交换更复杂。连续添加酸后电位变化的电化学测量表明，酸的共轭碱在整个反应过程中都起着至关重要的作用。计算表明，酸性氢最初与结合在金属上的TEhpp氮原子键合，然后，共轭碱向Mo-Mo键轴向位点的容易重排会同时导致氮原子的质子化。有趣的是，在此过程中，双金属络合物是双功能的，在TEhpp配体的氮原子上充当亲核试剂，在Mo-Mo轴向键合位置充当亲电试剂。质子化需要这些不同的键相互作用的新型协同作用，其中如果不通过配位基
• Increasing the solubility of strong reducing agents containing Mo24+ units and alkyl-substituted guanidinate ligands
  作者：F. Albert Cotton、Carlos A. Murillo、Xiaoping Wang、Chad C. Wilkinson

  DOI：10.1039/b707201e

  日期：——

  Six very soluble paddlewheel compounds containing Mo2n+ units, n = 4, 5, 6, and two alkyl-substituted bicyclic guanidinate ligands have been synthesized. The quadruply bonded complexes with n = 4, Mo2(TMhpp)4 and Mo2(TEhpp)4, (TMhpp = the anion of 3,3,9,9-tetramethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene and TEhpp = the anion of 3,3,9,9-tetraethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene) are easily oxidized. The electrode potentials in THF are −1.08 and −1.17 V vs. Ag/AgCl, respectively, for the Mo25+/4+ couple. These potentials are in accord with the low ionization potentials for the quadruply bonded compounds. Because of the high solubility of the Mo24+ compounds in most common organic solvents they are attractive candidates for use as strong reducing agents in homogeneous systems.

  合成了六种溶解度很高的桨轮化合物，其中含有 Mo2n+ 单元（n = 4、5、6）和两个烷基取代的双环胍配体。 n = 4、Mo2(TMhpp)4 和 Mo2(TEhpp)4 的四键配合物，（TMhpp = 3,3,9,9-四甲基-1,5,7-三氮杂双环[4.4.0]dec 的阴离子-4-ene和TEhpp = 3,3,9,9-四乙基-1,5,7-三氮杂双环[4.4.0]dec-4-ene的阴离子）很容易被氧化。对于 Mo25+/4+ 电对，THF 中的电极电位相对于 Ag/AgCl 分别为 -1.08 和 -1.17 V。这些电势与四键化合物的低电离电势一致。由于 Mo24+ 化合物在大多数常见有机溶剂中具有高溶解度，因此它们是在均相体系中用作强还原剂的有吸引力的候选者。
• Soluble paramagnetic Ru26+ paddlewheels with alkyl-substituted bicyclic guanidinates
  作者：Gina M. Chiarella、Carlos A. Murillo、Mark D. Young

  DOI：10.1016/j.poly.2015.07.031

  日期：2016.1

  Syntheses are reported for two diruthenium compounds having the formula Ru-2(TRhpp)(4)Cl-2, where R = Me (1) and Et (2) and TRhpp is the anion of a tetraalkyl-substituted bicyclic guanidinate. The Ru-2(6+) core of 1 is enclosed by four tetramethyl-substituted bicyclic guanidinates and two chlorine atoms positioned along the Ru-Ru axis. Each compound possesses two unpaired electrons at ambient temperature consistent with a formal bond order of three and a sigma(2)pi(4)delta(2)pi*(2) (Q(8)pi*(2)) electronic configuration. The compounds are EPR-silent as determined by examination of frozen dichloromethane solutions at 77 K using an X-band spectrometer. There is a short Ru-Ru distance of 2.2896(15) angstrom. Published by Elsevier Ltd.
• Solubilizing the Most Easily Ionized Molecules and Generating Powerful Reducing Agents
  作者：Gina M. Chiarella、F. Albert Cotton、Jason C. Durivage、Dennis L. Lichtenberger、Carlos A. Murillo

  DOI：10.1021/ja408291k

  日期：2013.11.27

  Two very soluble compounds having W-2(bicyclic guanidinate)(4) paddlewheel structures show record low ionization energies (onsets at 3.4 to 3.5 eV) and very negative oxidation potentials in THF (-1.84 to -1.90 V vs Ag/AgCl). DFT computations show the correlation from the gas-phase ionization energies to the solution redox potentials and chemical behavior. These compounds are thermally stable and easy to synthesize in high yields and good purity. They are very reactive and potentially useful stoichiometric reducing agents in nonpolar, nonprotonated solvents.