2,2'-偶氮二(5-氯嘧啶) | 215513-78-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 中文名称: 2,2'-偶氮二(5-氯嘧啶)
• 英文名称: 2,2′-azobis(5-chloropyrimidine)
• 英文别名: abcp；2,2'-azobis(5-chloropyrimidine)；2,2'-Azobis(5-chloropyrimidine)；bis(5-chloropyrimidin-2-yl)diazene
• CAS: 215513-78-3
• 化学式: C₈H₄Cl₂N₆
• 分子量: 255.066
• InChiKey: MKYFLPQUMMLDSJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  76.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  五羰基氯铼(I) 、 2,2'-偶氮二(5-氯嘧啶) 以 二氯甲烷 、 氯苯 为溶剂， 以79%的产率得到(μ-2,2'-azobis(5-chloropyrimidine))[Re(CO)3Cl]2
  参考文献：
  名称：

  Multifrequency EPR Study and Density Functional g-Tensor Calculations of Persistent Organorhenium Radical Complexes

  摘要：

  The dinuclear radical anion complexes {(mu-L)[Re(CO)(3)Cl](2)}(.-), L = 2,2'-azobispyridine (abpy) and 2,2'-azobis(5-chloropyrimidine) (abcp), were investigated by EPR at 9.5, 94, 230, and 285 GHz (abpy complex) and at 9.5 and 285 GHz (abcp complex). Whereas the X-band measurements yielded only the isotropic metal hyperfine coupling of the Re-185,Re-187 isotopes, the high-frequency EPR experiments in glassy frozen CH2Cl2/toluene solution revealed the g components. Both the a(Re-185,Re-187) value and the g anisotropy, g(1) - g(3), are larger for the abcp complex, which contains the better pi-accepting bridging ligand. Confirmation for this comes also from IR and UV/vis spectroscopy of the new {(mu-abcp)[Re(CO)(3)Cl](2)}(o/.-2/-) redox system. The g values are reproduced reasonably well by density functional calculations which confirm higher metal participation at the singly occupied MO and therefore larger contributions from the metal atoms to the g anisotropy in abcp systems compared to abpy complexes. Additional calculations for a series of systems {(mu-abcp)[M(CO)(3)X](2)}(.-) (M = Tc or Re and X = Cl, and X = F, Cl, or Br with M = Re) provided further insight into the relationship between spin density distribution and g anisotropy.

  DOI：

  10.1021/ja025829n

文献信息

• Multistep redox sequences of azopyridyl (L) bridged reaction centres in stable radical complex ions {(μ-L)[MCl(η⁵-C₅Me₅)]₂}˙⁺, M = Rh or Ir: spectroelectrochemistry and high-frequency EPR spectroscopy
  作者：Stéphanie Frantz、Ralf Reinhardt、Stefan Greulich、Matthias Wanner、Jan Fiedler、Carole Duboc-Toia、Wolfgang Kaim

  DOI：10.1039/b305311c

  日期：——

  The dinuclear complex cations (μ-L)[MCl(η5-C5Me5)]2}n, M = Rh or Ir and L = abpy (= 2,2′-azobispyridine) or abcp (= 2,2′-azobis(5-chloropyrimidine)), could be isolated as paramagnetic hexafluorophosphates (n = 1+) or, for M = Ir, as diamagnetic bis-hexafluorophosphates (n = 2+). In addition to the reversible one-electron process as indicated by this convertibility there are two successive chloride-releasing reduction steps, separated by unusually large potential differences ΔEEC between 0.75 V (Rh2/abpy) and 1.14 V (Ir2/abcp), leading to the spectroelectrochemically characterised complexes [(η5-Me5C5)M](μ-L)[MCl(η5-C5Me5)]}+ and (μ-L)[M(η5-C5Me5)]2. This large splitting of ΔEEC establishes the capability of azopyridyl bridges for mediating efficient metal–metal communication beyond mere electron transfer. The neutral complexes (μ-L)[M(η5-C5Me5)]2 are distinguished by a series of intense absorption bands in the near infrared, the lowest absorption energies being displayed by the Ir2/abcp combination. The stable electron reservoir intermediates (μ-L)[MCl(η5-C5Me5)]2}+ were identified as complexes of L˙− anion radicals via their small g anisotropy as measured through high-frequency (>200 GHz) EPR spectroscopy.

  双核络合物阳离子 (μ-L)[MCl(μ5-C5Me5)]2}n，M = Rh 或 Ir，L = abpy (= 2,2â²-偶氮二吡啶) 或 abcp (= 2,2â) ²-偶氮双(5-氯嘧啶))，可以作为顺磁性六氟磷酸盐分离(n = 1+) 或，对于 M = Ir，作为抗磁性双六氟磷酸盐 (n = 2+）。除了这种可转换性所表明的可逆单电子过程之外，还有两个连续的氯化物释放还原步骤，由 0.75 V (Rh2/abpy) 和 1.14 V (Ir2/abcp) 之间异常大的电势差 ΔEEC 隔开，导致光谱电化学表征的配合物 [(δ5-Me5C5)M](μ-L)[MCl(δ5-C5Me5)]}+ 和 (μ-L)[M(δ5-C5Me5)] 2. αEEC 的这种大分裂建立了偶氮吡啶桥的能力，它可以介导有效的金属间通讯，而不仅仅是电子转移。中性配合物(μ-L)[M(μ5-C5Me5)]2 的特点是在近红外区域有一系列强吸收带，Ir2/abcp 组合显示出最低的吸收能量。稳定电子库中间体(μ-L)[MCl(μ5-C5Me5)]2}+通过高频(>200 GHz）EPR 光谱。
• Low-Valence Triruthenium Compounds via Substitution of a Bridging Acetate in the Parent Ru₃O(OAc)₆ Cluster Core by 2,2‘-Azobispyridine (abpy) or 2,2‘-Azobis(5-chloropyrimidine) (abcp)
  作者：Heng-Yun Ye、Feng-Rong Dai、Li-Yi Zhang、Zhong-Ning Chen

  DOI：10.1021/ic0702771

  日期：2007.7.1

  of oxo-centered Ru(3)(III,III,III) precursor [Ru(3)O(OAc)(6)(py)(2)(CH(3)OH)](PF(6)) (1) with 1 equiv of 2,2'-azobispyridine (abpy) or 2,2'-azobis(5-chloropyrimidine) (abcp) induced the formation of stable Ru(3)(III,III,II) derivatives [Ru(3)O(OAc)(5)mu-eta(1)(N),eta(2)(N,N)-L}(py)(2)](PF(6)) (L = abpy (2), abcp (3)). As established in the structure of 3 by X-ray crystallography, 2 or 3 is derived

  以羰基为中心的Ru（3）（III，III，III）前体[Ru（3）O（OAc）（6）（py）（2）（CH（3）OH）]（PF（6））的反应（ 1）与1当量的2,2'-偶氮二吡啶（abpy）或2,2'-偶氮二（5-氯嘧啶）（abcp）诱导形成稳定的Ru（3）（III，III，II）衍生物[Ru（ 3）O（OAc）（5）mu-eta（1）（N），eta（2）（N，N）-L}（py）（2）]（PF（6））（L = abpy（ 2），abcp（3））。正如通过X射线晶体学在3的结构中确定的那样，2或3是通过用abpy取代母体Ru（3）O（OAc）（6）团簇核中的轴向甲醇和一种桥接乙酸盐而从1衍生而来的或abcp在mu-eta（1）（N），eta（2）（N，N）绑定模式下。肼还原3诱导单电子还原的中性Ru（3）（III，II，II）产物Ru（3）O（OAc）（5）mu-eta（1）（N），eta
• The First Structural Characterization of an Azoaromatic Radical Anion Stabilized by Dicopper(I) Coordination
  作者：Nataša Doslik、Torsten Sixt、Wolfgang Kaim

  DOI：10.1002/(sici)1521-3773(19980918)37:17<2403::aid-anie2403>3.0.co;2-j

  日期：1998.9.18

  Double chelate coordination of [Cu(Ph3 P)2 ]+ stabilizes the radical anion of 2,2'-azobis(5-chloropyrimidine), which exhibits a N-N bond length of 1.345(7) Å in the complex (see picture). This is consistent with a one-electron reduced azo functionality.

  [Cu（Ph 3 P）2 ] +的双重螯合配位稳定了2,2'-偶氮双（5-氯嘧啶）的自由基阴离子，该络合物在络合物中的NN键长为1.345（7）Å（参见图片） 。这与单电子还原的偶氮功能一致。
• Mixed-Valent Metals Bridged by a Radical Ligand:  Fact or Fiction Based on Structure-Oxidation State Correlations
  作者：Biprajit Sarkar、Srikanta Patra、Jan Fiedler、Raghavan B. Sunoj、Deepa Janardanan、Goutam Kumar Lahiri、Wolfgang Kaim

  DOI：10.1021/ja077676f

  日期：2008.3.1

  Electron-rich Ru(acaC)(2) (acac(-) = 2,4-pentanedionato) binds to the pi electron-deficient bis-chelate ligands L, L = 2,2'-azobispyridine (abpy) or azobis(5-chloropyrimidine) (abcp), with considerable transfer of negative charge. The compounds studied, (abpy)Ru(acac)(2) (1), meso-(mu-abpy)[Ru(acaC)(2)](2) (2), rac-(mu-abpy)[Ru(acac)(2)](2) (3), and (mu-abcp)[Ru(acac)(2)](2) (4), were calculated by DFT to assess the degree of this metal-to-ligand electron shift. The calculated and experimental structures of 2 and 3 both yield about 1.35 angstrom for the length of the central N-N bond which suggests a monoanion character of the bridging ligand. The NBO analysis confirms this interpretation, and TD-DFT calculations reproduce the observed intense long-wavelength absorptions. While mononuclear 1 is calculated with a lower net ruthenium-to-abpy charge shift as illustrated by the computed 1.30 angstrom for d(N-N), compound 4 with the stronger pi accepting abcp bridge is calculated with a slightly lengthened N-N distance relative to that of 2. The formulation of the dinuclear systems with monoanionic bridging ligands implies an obviously valence-averaged (RuRuII)-Ru-III mixed-valent state for the neutral molecules. Mixed valency in conjunction with an anion radical bridging ligand had been discussed before in the discussion of MLCT excited states of symmetrically dinuclear coordination compounds. Whereas 1 still exhibits a conventional electrochemical and spectroelectrochemical behavior with metal centered oxidation and two ligand-based one-electron reduction waves, the two one-electron oxidation and two one-electron reduction processes for each of the dinuclear compounds Ru-2.5(L*(-))Ru-2.5 reveal more unusual features via EPR and UV-vis-NIR spectroelectrochemistry. In spite of intense near-infrared absorptions, the EPR results show that the first reduction leads to Ru-II(L*(-))Ru-II species, with an increased metal contribution for system 4*(-). The second reduction to Ru-II(L2-)Ru-II causes the disappearance of the NIR band. One-electron oxidation of the Ru-2.5(L*(-)) Ru-2.5 species produces a metal-centered spin for which the alternatives Ru-III(L-0)Ru-II or Ru-III(L*(-))Ru-III can be formulated: The absence of NIR bands as common for mixed-valent species with intervalence charge transfer (IVCT) absorption favors the second alternative. The second one-electron oxidation is likely to produce a dication with Ru-III(L-0)Ru-III formulation. The usefulness and limitations of the increasingly popular structure/oxidation state correlations for complexes with noninnocent ligands is being discussed.
• A Ligand-Bridged Heterotetranuclear (Fe₂Cu₂) Redox System with Fc/Fc⁺ and Radical Ion Intermediates
  作者：Rajkumar Jana、Falk Lissner、Brigitte Schwederski、Jan Fiedler、Wolfgang Kaim

  DOI：10.1021/om400466u

  日期：2013.10.28

  The redox pair [(mu-abcp)Cu(dppf)}(2)](2+/+) (abcp = 2,2'-azobis(5-chloropyrimidine) and dppf = 1,1'-bis(diphenylphosphino)ferrocene) has been structurally characterized to reveal the lengthening of the NN and shortening of the CNazo bonds on reduction, each by about 0.04 angstrom. These and other charge forms, [(mu-abcp)Cu(dppf)}(2)](n+) (n = 0, 3+, 4+), have been investigated spectroelectrochemically (UV-vis-near-IR, EPR) to reveal an abcp-based second reduction and a stepwise ferrocene-centered oxidation of the 2+ precursor. In contrast to the small but detectable comproportionation constant of K-c = 17 for the Fc/Fc(+) mixed-valence (3+) charge state, the monocationic radical complex exhibits a very large K-c value of 10(16).