6-(吡啶-2-基)-[2,2'-联吡啶]-4-腈 | 81874-54-6

• 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
• 中文名称: 6-(吡啶-2-基)-[2,2'-联吡啶]-4-腈
• 英文名称: 2,6-bis(2-pyridinyl)-pyridine-4-carbonitrile
• 英文别名: 4'-cyano-2,2':6',2''-terpyridine；4'-cyano-2,2':6',2"-terpyridine；tpyCN；6-(Pyridin-2-yl)-[2,2'-bipyridine]-4-carbonitrile；2,6-dipyridin-2-ylpyridine-4-carbonitrile
• CAS: 81874-54-6
• 化学式: C₁₆H₁₀N₄
• 分子量: 258.282
• InChiKey: KALLUAMTZFFSDE-UHFFFAOYSA-N

物化性质

• 熔点：
  168-169 °C
• 沸点：
  438.7±45.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  62.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  iron(II) chloride tetrahydrate 、 6-(吡啶-2-基)-[2,2'-联吡啶]-4-腈 以 水 、 乙腈 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  量子化学辅助的配体工程用于潜在的分子开关：改变势垒以调节激发态寿命

  摘要：

  用吸电子和供电子基团取代4'位置上的三联吡啶用于调整其铁（II）配合物的五联体寿命。DFT计算表明，五重态和单重态之间的能垒可以在取代时显着改变，从而引起光激发五重态的寿命发生较大变化。该预测已通过瞬态光吸收光谱法进行了实验验证，并与计算预期的趋势很好地吻合。这表明通过基于DFT预测的相关修改，确实可以合理地调整潜在的能源格局。该结果应为将有效的基于理论的功能分子配体工程推进到广泛的应用铺平道路。

  DOI：

  10.1039/d0cc04467a
• 作为产物：
  描述：

  4'-(甲硫基)-2,2':6',2''-三联吡啶 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 生成 6-(吡啶-2-基)-[2,2'-联吡啶]-4-腈
  参考文献：
  名称：

  Synthesis of 2,6-disubstituted pyridines, polypyridinyls, and annulated pyridines

  摘要：

  DOI：

  10.1021/jo00137a001

文献信息

• The Synthesis of Poly-Nitrile Aromatic and Oligopyridine Ligands Via Palladium-Catalyzed Cyanation of Aryl Halides
  作者：Kevin John、Jacqueline Veauthier、Christin Carlson、Gavin Collis、Jaqueline Kiplinger

  DOI：10.1055/s-2005-872113

  日期：——

  Modification of Beller's palladium-catalyzed cyanation procedure for simple aromatic halides leads to a versatile and rapid route to complex multi-nitrile aryl and oligopyridyl ligands that improves on known literature methods. By heating the reagents in the high boiling solvent mesitylene to reflux temperatures at ambient pressure, we have observed the conversion of halogenated precursors to the corresponding

  Beller 对简单芳族卤化物的钯催化氰化过程的改进导致了一种通用且快速的复杂多腈芳基和寡吡啶基配体的路线，该路线改进了已知的文献方法。通过在环境压力下将高沸点溶剂均三甲苯中的试剂加热至回流温度，我们观察到卤代前体转化为相应的腈化合物。所得化合物可以从反应混合物的 CH 2 Cl 2 溶液中沉淀出来，并以中等至高产率分离为纯化合物。目前的方法为压力管方法提供了一种更安全的替代方法，因为它不涉及在高压下使用 KCN。
• Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide and Lanthanoid-Actinide Complexes Possessing Redox-Active Bridging Ligands
  作者：Eric J. Schelter、Ruilian Wu、Jacqueline M. Veauthier、Eric D. Bauer、Corwin H. Booth、Robert K. Thomson、Christopher R. Graves、Kevin D. John、Brian L. Scott、Joe D. Thompson、David E. Morris、Jaqueline L. Kiplinger

  DOI：10.1021/ic9024475

  日期：2010.2.15

  peripheral “M” site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic YbIII-UIV-YbIII, SmIII-UIV-SmIII, and LaIII-UIV-LaIII complexes, [8]−, [9b]−, and [10b]−, respectively

  提出了一系列三金属act系元素以及镧系-act系元素和镧系-act系元素配合物的电子相互作用的比较研究。使用还原的自由基叔吡啶基配体作为桥联框架中的管道，以促进分子内金属与金属之间的连通，报道了有关（C 5 Me 5）2 An [-N═C（Bn ）的研究，包括结构，电化学和X射线吸收光谱）（tpy-M C 5 Me 4 R} 2）] 2（其中An = Th IV，U IV ; Bn = CH 2 C 6 H 5 ; M = La III，Sm III，Yb III，U III ; R = H，Me，Et）以揭示取决于金属离子和R-基团身份的效应。电化学结果表明，配合物之间的外围“ M”位处的氧化还原能量存在差异，并且基于金属和配体的过程发生了明显的波分裂，表明整个含act系元素的氧化还原位点之间存在大量电子相互作用。最引人注目的是强电子耦合的用于三金属镱外观III -U IV -Yb III，钐III
• Copper(II) Complexes of 2,2′:6′,2″‐Terpyridine Derivatives for Catalytic Aerobic Alcohol Oxidations – Observation of Mixed‐Valence Cu ^I Cu ^II Assembles
  作者：Guoqi Zhang、E Liu、Chengxiong Yang、Li Li、James A. Golen、Arnold L. Rheingold

  DOI：10.1002/ejic.201403140

  日期：2015.2

  solutions of tpy derivatives with copper dichloride. Two new complexes with interesting solid-state structures resulting from these reactions have been isolated and characterized. The coordination reactions in the presence of TEMPO led to new mixed-valence CuICuII supramolecular assembles (4 and 5), although they adopt either discrete complex or 1D polymeric structures. Further catalytic studies indicated

  铜 (II) 盐与简单的三联吡啶 (tpy) 配体反应得到单核单配体配合物 1-3，其中两个新结构已通过 X 射线晶体学表征。在2,2,6,6-四甲基哌啶基-1-氧基（TEMPO）存在下，这些配合物被用作在空气中将苯甲醇氧化成苯甲醛的催化剂。铜配合物 1 和 2 是在 70 °C 水中以 4-二甲氨基吡啶 (DMAP) 作为额外碱进行反应的有效催化剂。通过将TEMPO引入tpy衍生物与二氯化铜的反应溶液中，初步研究了TEMPO对催化反应过程中新反应中间体形成的影响。已经分离并表征了由这些反应产生的具有有趣固态结构的两种新配合物。TEMPO 存在下的配位反应导致了新的混合价 CuICuII 超分子组装（4 和 5），尽管它们采用离散复合物或一维聚合物结构。进一步的催化研究表明，在较温和的条件下，混合价组装 4 和 5 显示出比单核配合物更高的催化活性。在所得结果的基础上讨论了不同铜配合物的分
• Observation of Internal Electron Transfer in Bulky Allyl Ytterbium Complexes with Substituted Terpyridine Ligands
  作者：Rosemary E. White、Christin N. Carlson、Jacqueline M. Veauthier、Cheslan K. Simpson、J. D. Thompson、Brian L. Scott、Timothy P. Hanusa、Kevin D. John

  DOI：10.1021/ic060603x

  日期：2006.8.1

  A series of new bulky allyl terpyridyl-ytterbium complexes have been synthesized to determine the effect of allyl ligands on the internal charge-transfer process that exists in these materials. Compared to the pentamethylcyclopentadienyl-ytterbocene compound Cp*Yb-2(tpyCN) (nu(C N) = 2172 cm(-1)), the symmetrically substituted allyl complex [1,3-(SiMe3)(2)C3H3](2)Yb(tpyCN) possesses a markedly lowered C N frequency of 2130 cm(-1). Furthermore, the electronic nature of these bulky allyl complexes can be tuned, as demonstrated by the C N frequency of the asymmetric derivatives [1-(SiMe3)C3H4]2Yb(tpyCN) and [1-(SiPh3)-3-(SiMe3)C3H3](2)Yb(tpyCN) (2171 and 2164 cm(-1), respectively). The differences in these frequencies can be attributed to differences in the ligands' steric and electronic character. Single-crystal X-ray characterization of [1,3-(SiMe3)(2)C3H3](2)Yb(tpy) reveals that the allyl moiety possesses shorter Yb-C and Yb-N bond distances than the Cp* analogue. The magnetic susceptibility data for [1,3-(SiMe3)(2)C3H3](2)Yb(tpy) departs dramatically from the Curie law, with a room-temperature magnetic moment of 2.95 mu(B).
• Ligand Substituent Effect Observed for Ytterbocene 4‘-Cyano-2,2‘:6‘,2‘ ‘-terpyridine
  作者：Jacqueline M. Veauthier、Eric J. Schelter、Christopher J. Kuehl、Aurora E. Clark、Brian L. Scott、David E. Morris、Richard L. Martin、J. D. Thompson、Jaqueline L. Kiplinger、Kevin D. John

  DOI：10.1021/ic050148p

  日期：2005.8.1

  A new N-heterocyclic complex of ytterbocene (Cp*Yb-2(II), CP* = C5Me5) has been prepared by the addition of 4'-cyano-2,2':6',2"-terpyridine (tpyCN) to CP*Yb-2(II)(OEt2) in toluene to give a dark blue species designated as CP*Yb-2(tpyCN). The effect of the electron-withdrawing group (-C equivalent to N) on the redox potentials of the charge-transfer form of this complex [in which an electron is transferred from the f(14) metal center to the lowest unoccupied (pi*) molecular orbital of the tpyCN ligand to give a 4f(13)-pi*(1) electronic configuration] has been quantified by cyclic voltammetry. The tpyCN ligand stabilizes this configuration by 60 mV more than that in the unsubstituted tpy ligand complex and by 110 mV more than that in the unsubstituted bpy ligand complex. Magnetic susceptibility measurements corroborate the enhanced stabilization of the 4f(13)-pi*(1) configuration by the substituted terpyridyl ligand complex. Furthermore, the temperature dependence of the magnetic data is most consistent with a thermally induced valence tautomeric equilibrium between this paramagnetic 4f(13)-pi*(1) form that dominates near room temperature and the diamagnetic 4f(14)-pi*(0) form that dominates at low temperature. Differing coordination modes for the tpyCN ligand to the ytterbocene center have also been confirmed by isolation and X-ray crystallographic characterization of complexes binding through either the cyano nitrogen of tpyCN or the three terpyridyl nitrogen atoms of tpyCN.