2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline | 1276186-76-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline
• 英文别名: 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo[e][1,2,4]triazin-3-yl)-1,10-phenanthroline；2,9-Bis(5,5,8,8-tetramethyl-6,7-dihydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline；2,9-bis(5,5,8,8-tetramethyl-6,7-dihydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline
• CAS: 1276186-76-5
• 化学式: C₃₄H₃₈N₈
• 分子量: 558.729
• InChiKey: GFQVTGCFMNWLNU-UHFFFAOYSA-N

物化性质

• 沸点：
  775.6±70.0 °C(Predicted)
• 密度：
  1.160±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  42
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  103
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline 在 高氯酸 作用下， 以 甲醇 、 水 为溶剂， 生成
  参考文献：
  名称：

  Complexation of Cm(iii) and Eu(iii) with CyMe₄-BTPhen and CyMe₄-BTBP studied by time resolved laser fluorescence spectroscopy

  摘要：

  Cm(III)和Eu(III)与2,9-双(5,5,8,8-四甲基-5,6,7,8-四氢-1,2,4-苯并三嗪-3-基)-1,10-菲罗啉(CyMe4-BTPhen)和6、TRLFS 对甲醇溶液中的 6、6′-双（5,5,8,8-四甲基-5,6,7,8-四氢-1,2,4-苯并三嗪-3-基）-2,2′-联吡啶（CyMe4-BTBP）进行了研究。对于这两种配体，与特定金属离子的 1:2 复合物是在平衡样品中观察到的唯一物种。测定了不同配体浓度下的物种分布，并得出了 1:2 复合物的稳定常数（log β2 = 13.8 ± 0.2（Cm(III)-CyMe4-BTPhen）、log β2 = 11.6 ± 0.4（Eu(III)-CyMe4-BTPhen）、log β2 = 12.4 ± 0.3（Cm(III)-CyMe4-BTBP）和 log β2 = 11.3 ± 0.3（Eu(III)-CyMe4-BTBP））。结合有机相 TRLFS 研究进行的双相实验显示，在萃取过程中形成了具有两个 CyMe4-BTPhen 或 -BTBP 分子的三元络合物，并额外配位了一个硝酸根阴离子。

  DOI：

  10.1039/c3dt52204k
• 作为产物：
  描述：

  1,10-phenanthroline-2,9-dicarboxaldehyde-2,9-dioxime 在 乙酸酐 、 一水合肼 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 410.0h， 生成 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline
  参考文献：
  名称：

  Highly Efficient Separation of Actinides from Lanthanides by a Phenanthroline-Derived Bis-triazine Ligand

  摘要：

  The synthesis, lanthanide complexation, and solvent extraction of actinide(III) and lanthanide(III) radiotracers from nitric acid solutions by a phenanthroline-derived quadridentate bis-triazine ligand are described. The ligand separates Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity, and fast extraction kinetics compared to its 2,2'-bipyridine counterpart. Structures of the 1:2 bis-complexes of the ligand with Eu(III) and Yb(III) were elucidated by X-ray crystallography and force field calculations, respectively. The Eu(III) bis-complex is the first 1:2 bis-complex of a quadridentate bis-triazine ligand to be characterized by crystallography. The faster rates of extraction were verified by kinetics measurements using the rotating membrane cell technique in several diluents. The improved kinetics of metal ion extraction are related to the higher surface activity of the ligand at the phase interface. The improvement in the ligand's properties on replacing the bipyridine unit with a phenanthroline unit far exceeds what was anticipated based on ligand design alone.

  DOI：

  10.1021/ja203378m

文献信息

• Exploring electronic effects on the partitioning of actinides(<scp>iii</scp>) from lanthanides(<scp>iii</scp>) using functionalised bis-triazinyl phenanthroline ligands
  作者：Alyn C. Edwards、Christoph Wagner、Andreas Geist、Neil A. Burton、Clint A. Sharrad、Ralph W. Adams、Robin G. Pritchard、Petra J. Panak、Roger C. Whitehead、Laurence M. Harwood

  DOI：10.1039/c6dt02474b

  日期：——

  5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzo-triazin-3-yl)-1,10-phenanthroline (CyMe4-BTPhen) ligands are reported herein. Evaluating the kinetics, selectivity and stoichiometry of actinide(III) and lanthanide(III) radiotracer extractions has provided a mechanistic insight into the extraction process. For the first time, it has been demonstrated that metal ion extraction kinetics can be modulated

  4,7-二取代的2,9-双（5,5,8,8-四甲基-5,6,7,8-四氢-1,2,4-苯并三嗪-3-基）的第一个例子本文报道了1，10-菲咯啉（CyMe 4 -BTPhen）配体。评估动力学，选择性和锕系元素的化学计量（III）和镧系元素（III）的放射性示踪剂提取提供了对提取过程的机械洞察力。首次证明，可以通过主链官能团调节金属离子的萃取动力学，并且已经鉴定出具有增强的金属离子萃取动力学的有希望的新的符合CHON的候选配体。4,7-官能化对平衡金属离子分布比的影响远比5,6-官能化的影响更为明显。通过TRLFS研究了Cm（III）与两个官能化配体的络合，并且在平衡时仅观察到化学计量为1：2 [M：L]的物种。E LUMO – E HOMO之间的直接关联 报告了能隙和金属离子的提取潜力，DFT研究证实了实验结果。
• Plutonium coordination and redox chemistry with the CyMe₄-BTPhen polydentate N-donor extractant ligand
  作者：Sean D. Reilly、Jing Su、Jason M. Keith、Ping Yang、Enrique R. Batista、Andrew J. Gaunt、Laurence M. Harwood、Michael J. Hudson、Frank W. Lewis、Brian L. Scott、Clint A. Sharrad、Daniel M. Whittaker

  DOI：10.1039/c8cc06015k

  日期：——

  Complexation of Pu(IV) with the actinide extractant CyMe4-BTPhen (2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline) was followed by vis-NIR spectroscopy in acetonitrile solution. The solid-state structure of the crystallized product suggests that Pu(IV) is reduced to Pu(III) upon complexation. Analysis by DFT modeling is consistent with metal-based rather

  Pu（IV）与the系元素萃取剂CyMe 4 -BTPhen（2,9-bis（5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3 （-yl）-1,10-菲咯啉），然后在乙腈溶液中进行vis-NIR光谱分析。结晶产物的固态结构表明，Pu（IV）在络合后被还原为Pu（III）。通过DFT建模进行的分析与基于金属的还原而不是基于配体的还原相一致。
• Effective separation of the actinides Am(<scp>iii</scp>) and Cm(<scp>iii</scp>) by electronic modulation of bis-(1,2,4-triazin-3-yl)phenanthrolines
  作者：Ashfaq Afsar、Laurence M. Harwood、Michael J. Hudson、James Westwood、Andreas Geist

  DOI：10.1039/c5cc00567a

  日期：——

  It has been shown that modification of the phenanthroline backbone of CyMe₄-BTPhen leads to subtle electronic modulation, permitting differential ligation of Am(iii) and Cm(iii) resulting in separation factors up to 7.

  已经表明，修改CyMe₄-BTPhen的菲啰啉骨架可以进行微妙的电子调节，从而允许Am(iii)和Cm(iii)的差异配位，导致分离因子高达7。
• Lanthanide Speciation in Potential SANEX and GANEX Actinide/Lanthanide Separations Using Tetra-N-Donor Extractants
  作者：Daniel M. Whittaker、Tamara L. Griffiths、Madeleine Helliwell、Adam N. Swinburne、Louise S. Natrajan、Frank W. Lewis、Laurence M. Harwood、Stephen A. Parry、Clint A. Sharrad

  DOI：10.1021/ic301599y

  日期：2013.4.1

  is dominant in solution. X-ray absorption spectra of Eu3+ and Tb3+ species, formed by extraction from an acidic aqueous phase into an organic solution consisting of excess N-donor extractant in pure cyclohexanone or 30% tri-n-butyl phosphate (TBP) in cyclohexanone, were obtained. The presence of TBP in the organic phase did not alter lanthanide speciation. Extended X-ray absorption fine structure data

  已直接合成并在溶液和固态下表征了具有N-给体萃取剂的镧系元素（III）配合物，该配合物在从乏燃料中处理中可从镧系元素中分离出少量act系元素。镨的晶体结构3+，Eu的3+，Tb的3+和Yb 3+的2,9-双（5,5,8,8-四甲基-5,6,7,8-四氢- 1复合物， 2,4-苯并三嗪-3-基）-1,10-菲咯啉（CyMe 4 -BTPhen）和6,6'-bis（5,5,8 ）的Pr 3+，Eu 3+和Tb 3+络合物，8-四甲基-5,6,7,8-四氢-1,2,4-苯并三嗪-3-基）-2,2'-吡啶（CyMe 4-BTBP）。即使在某些情况下，用等摩尔量的镧系元素和N-供体配体进行络合，这些结构中的大多数仍显示出两个L-N 3+离子配位有两个四-N-供体配体。结构表明，一般来说，较轻的镧系元素的配位球是由双齿硝酸盐离子完成的，产生带2+电荷的复合阳离子，而较重的镧系元素的结构表现为三阳离子复
• BTBPs versus BTPhens: Some Reasons for Their Differences in Properties Concerning the Partitioning of Minor Actinides and the Advantages of BTPhens
  作者：Frank W. Lewis、Laurence M. Harwood、Michael J. Hudson、Michael G. B. Drew、Véronique Hubscher-Bruder、Vladimira Videva、Françoise Arnaud-Neu、Karel Stamberg、Shyam Vyas

  DOI：10.1021/ic3026842

  日期：2013.5.6

  Two members of the tetradentate N-donor ligand families 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) currently being developed for separating actinides from lanthanides have been studied. It has been confirmed that CyMe4-BTPhen 2 has faster complexation kinetics than CyMe4-BTBP 1. The values for the HOMO-LUMO gap of 2 are comparable with those of CyMe4-BTBP 1 for which the HOMO-LUMO gap was previously calculated to be 2.13 eV. The displacement of BTBP from its bis-lanthanum(III) complex by BTPhen was observed by NMR, and constitutes the only direct evidence for the greater thermodynamic stability of the complexes of BTPhen. NMR competition experiments suggest the following order of bis-complex stability: 1:2 bis-BTPhen complex >= heteroleptic BTBP/BTPhen 1:2 bis-complex > 1:2 bis-BTBP complex. Kinetics studies on some bis-triazine N-donor ligands using the stopped flow technique showed a clear relationship between the rates of metal ion complexation and the degree to which the ligand is preorganized for metal binding. The BTBPs must overcome a significant (ca. 12 kcal mol(-1)) energy barrier to rotation about the central biaryl C-C axis in order to achieve the cis-cis conformation that is required to form a complex, whereas the cis-cis conformation is fixed in the BTPhens. Complexation thermodynamics and kinetics studies in acetonitrile show subtle differences between the thermodynamic stabilities of the complexes formed, with similar stability constants being found for both ligands. The first crystal structure of a 1:1 complex of CyMe4-BTPhen 2 with Y(NO3)(3) is also reported. The metal ion is 10-coordinate being bonded to the tetradentate ligand 2 and three bidentate nitrate ions. The tetradentate ligand is nearly planar with angles between consecutive rings of 16.4(2)degrees, 6.4(2)degrees, 9.7(2)degrees, respectively.