3,6-bis-(5-methyl-2-pyridine)-1,2,4,5-tetrazine | 1112989-31-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 3,6-bis-(5-methyl-2-pyridine)-1,2,4,5-tetrazine
• 英文别名: 3,6-bis(5-methyl-2-pyridine)-1,2,4,5-tetrazine；3,6-bis(5-methyl-2-pyridine)1,2,4,5-tetrazine；3,6-(5-methyl-pyridyl)-1,2,4,5-tetrazine；Me2BPTZ；3,6-Bis(5-methylpyridin-2-yl)-1,2,4,5-tetrazine；3,6-bis(5-methylpyridin-2-yl)-1,2,4,5-tetrazine
• CAS: 1112989-31-7
• 化学式: C₁₄H₁₂N₆
• 分子量: 264.289
• InChiKey: DAKGEGKDFOJFMM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  77.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,6-bis-(5-methyl-2-pyridine)-1,2,4,5-tetrazine 、 乙炔 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 以98%的产率得到2,5-bis-(5-methyl-2-pyridine)-pyridazine
  参考文献：
  名称：

  Bilability is Defined when One Electron is Used to Switch between Concerted and Stepwise Pathways in Cu(I)-Based Bistable [2/3]Pseudorotaxanes

  摘要：

  Supramolecular switches operate as simple machines by using a stimulus to turn stations off and on, generating thermodynamic differences that define bistability and enable motion. What has not been previously investigated, yet is required to gain further control over molecular movements for complex operations, is an understanding of how the same stimulus can also switch pathways off and on, thus, defining the kinetic property of bilability. To address this challenge, the mechanisms of the forward and return reactions of redox-switchable Cu(I)-based [2/3]pseudorotaxanes have been quantitatively characterized utilizing mechanistic cyclic voltammetry and employing a series of isosteric bis-bidentate ligands. First, the bistability of the switch is retained across the series of ligands: Reduction of the ligand drives the reaction forward where a [2]pseudorotaxane switches into a reduced [3]pseudorotaxane and reoxidation drives the switching cycle back to the beginning. Second, the switch is bilabile with the forward reaction following an association-activated interchange pathway (concerted), whereas the reverse reaction follows a different dissociation-based dethreading pathway (stepwise). The forward reaction is more sensitive to denticity (bidentate tetrazinyl ligand, k(2) = 12 000 M-1 s(-1), versus the monodentate pyrazinyl ligand, k(2) = 1500 M-1 s(-1)) than to electronics (k(2) = 12 000 M-1 s(-1) for methyl and trifluoromethyl substituents). The rate of return with the pyrazinyl ligand is k(1) = 50 s(-1). Consequently, both the mechanism and the thermodynamics of switching are stimuli dependent; they change with the oxidation state of the ligand. These findings have implications for the future design of molecular motors, which can be built from systems displaying allosterically coupled bistability and bilability.

  DOI：

  10.1021/ja908877d
• 作为产物：
  描述：

  2-氰基-5-甲基吡啶 在 sulfur 、 肼 、 溶剂黄146 、 sodium nitrite 作用下， 以 乙醇 、 水 为溶剂， 反应 12.0h， 以49%的产率得到3,6-bis-(5-methyl-2-pyridine)-1,2,4,5-tetrazine
  参考文献：
  名称：

  McNitt, Kristy A.; Parimal, Kumar; Share, Andrew I., Journal of the American Chemical Society, 2009, vol. 131, p. 1305 - 1313

  摘要：

  DOI：

文献信息

• Bond elongation in the anion radical of coordinated tetrazine ligands: A crystallographic, spectroscopic and computational study of a reduced {Re(CO)3Cl} complex
  作者：Kumar Parimal、Shubham Vyas、Chun-Hsing Chen、Christopher M. Hadad、Amar H. Flood

  DOI：10.1016/j.ica.2011.05.005

  日期：2011.8

  The binuclear complex [(mu-Me(2)BPTZ)(Re(CO)(3)Cl)(2)] (1), where Me(2)BPTZ = 3,6-(5-methyl-pyridyl)-1,2,4,5-tetrazine, can be reduced by addition of bis(eta(5)-pentamethylcyclopentadienyl) iron(II) (decamethylferrocene, Fc*), to obtain a stable radical anion form 1(.). A single-crystal X-ray diffraction study of the radical anion (1(.))(Fc*(+)) was conducted and compared with a computational model of the same compound in the neutral and reduced states. As such, this work presents the first structural analysis of a reduced diimine ligand that is coordinated to Re(CO)(3)Cl} moieties. Bond-length changes within the tetrazine ring system were consistent with previously reported examples of tetrazine radicals and with calculated structures that show clear elongation of the azo-type N=N bond. Consistently atomic charge calculations indicate that the extra electron in the radical anion resides largely at the tetrazine core. A negligible change in the Re-Cl bond length is observed and computed. (C) 2011 Elsevier B.V. All rights reserved.
• Bilability is Defined when One Electron is Used to Switch between Concerted and Stepwise Pathways in Cu(I)-Based Bistable [2/3]Pseudorotaxanes
  作者：Andrew I. Share、Kumar Parimal、Amar H. Flood

  DOI：10.1021/ja908877d

  日期：2010.2.10

  Supramolecular switches operate as simple machines by using a stimulus to turn stations off and on, generating thermodynamic differences that define bistability and enable motion. What has not been previously investigated, yet is required to gain further control over molecular movements for complex operations, is an understanding of how the same stimulus can also switch pathways off and on, thus, defining the kinetic property of bilability. To address this challenge, the mechanisms of the forward and return reactions of redox-switchable Cu(I)-based [2/3]pseudorotaxanes have been quantitatively characterized utilizing mechanistic cyclic voltammetry and employing a series of isosteric bis-bidentate ligands. First, the bistability of the switch is retained across the series of ligands: Reduction of the ligand drives the reaction forward where a [2]pseudorotaxane switches into a reduced [3]pseudorotaxane and reoxidation drives the switching cycle back to the beginning. Second, the switch is bilabile with the forward reaction following an association-activated interchange pathway (concerted), whereas the reverse reaction follows a different dissociation-based dethreading pathway (stepwise). The forward reaction is more sensitive to denticity (bidentate tetrazinyl ligand, k(2) = 12 000 M-1 s(-1), versus the monodentate pyrazinyl ligand, k(2) = 1500 M-1 s(-1)) than to electronics (k(2) = 12 000 M-1 s(-1) for methyl and trifluoromethyl substituents). The rate of return with the pyrazinyl ligand is k(1) = 50 s(-1). Consequently, both the mechanism and the thermodynamics of switching are stimuli dependent; they change with the oxidation state of the ligand. These findings have implications for the future design of molecular motors, which can be built from systems displaying allosterically coupled bistability and bilability.
• McNitt, Kristy A.; Parimal, Kumar; Share, Andrew I., Journal of the American Chemical Society, 2009, vol. 131, p. 1305 - 1313
  作者：McNitt, Kristy A.、Parimal, Kumar、Share, Andrew I.、Fahrenbach, Albert C.、Witlicki, Edward H.、et al.

  DOI：——

  日期：——