6-(2-Bromophenyl)-2,2'-bipyridine

• 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: 6-(2-Bromophenyl)-2,2'-bipyridine
• 英文别名: 2-(2-Bromophenyl)-6-pyridin-2-ylpyridine；2-(2-bromophenyl)-6-pyridin-2-ylpyridine
• 化学式: C₁₆H₁₁BrN₂
• 分子量: 311.181
• InChiKey: XEBDDHGCCHXGLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 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：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-(2-Bromophenyl)-2,2'-bipyridine 以 四氢呋喃 为溶剂， 反应 40.0h， 生成
  参考文献：
  名称：

  X 配体在环金属化 [Ni(Phbpy)X] 配合物中的作用 (HPhbpy = 6-Phenyl-2,2'-bipyridine)

  摘要：

  携带阴离子三齿 C ∧ N ∧ N 配体 6-(phen-2-ide ) 的有机镍配合物 [Ni(Phbpy)X] (X = F, Cl, Br, I, C 6 F 5 ) 中的共配体X )-2,2'-联吡啶 (Phbpy – ) 研究其对这些配合物的电子结构的影响及其在 Negishi 样 C-C 交叉偶联催化中的活性。该配合物由前体 [Ni(COD) 2]（COD = 1,5-环辛二烯）通过螯合物辅助氧化加成到原配体 6-（2-卤代苯基）-2,2'-联吡啶的苯基 C-X 键中）并以红色粉末形式获得。携带卤化物替代物 X = OMe、OTf（三氟甲磺酸盐）的原配体 X–Phbpy 在该反应中失败。单晶 XRD 使我们能够将 [Ni(Phbpy)Cl] 和 [Ni(Phbpy)I] 的结构添加到先前报道的 Br 衍生物中。循环伏安法显示出对X = C可逆减少6 ˚F 5，氟，氯，而Br和I

  DOI：

  10.1021/acs.organomet.1c00237
• 作为产物：
  描述：

  6-苯基-2,2'-联吡啶 在 N-溴代丁二酰亚胺(NBS) 、 palladium diacetate 作用下， 以 乙腈 为溶剂， 反应 14.0h， 以93%的产率得到6-(2-Bromophenyl)-2,2'-bipyridine
  参考文献：
  名称：

  The cyclometalated nickel complex [(Phbpy)NiBr] (Phbpy− = 2,2′-bipyridine-6-phen-2-yl) – Synthesis, spectroscopic and electrochemical studies

  摘要：

  The new organometallic nickel complex [(Phbpy)NiBr] containing the anionic tridentate N,N,C ligand 6-(phen-2-yl)-2,2'-bipyridine (Phbpy) was synthesised from PhbpyBr and [Ni(COD)(2)] in excellent yields and was fully characterised (MS, NMR, single crystal XRD). [(Phbpy) NiBr] was reacted with (CF3)SiMe3 giving the CF3 complex [(Phbpy)Ni(CF3)]. Both new complexes were studied in detail by electrochemical (CV) and spectroelectrochemical (UV/vis/NIR absorption) methods. For both complexes the first one-electron reduction and the first oxidation of the Br complex occur fully reversible in the CV, while spectroelectrochemistry shows decomposition reactions. The CF3 complex is unstable in solution producing 2-CF3-Phbpy. Reactivity patterns for these reactions were discussed, also in comparison with the non-cyclometalated complex [(bpy)Ni(Mes)Br]. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2014.10.013

文献信息

• Excited‐State Kinetics of an Air‐Stable Cyclometalated Iron(II) Complex
  作者：Jakob Steube、Lukas Burkhardt、Ayla Päpcke、Johannes Moll、Peter Zimmer、Roland Schoch、Christoph Wölper、Katja Heinze、Stefan Lochbrunner、Matthias Bauer

  DOI：10.1002/chem.201902488

  日期：2019.9.12

  The complex class [Fe(N^N^C)(N^N^N)]+ with an Earth-abundant metal ion has been repeatedly suggested as a chromophore and potential photosensitizer on the basis of quantum chemical calculations. Synthesis and photophysical properties of the parent complex [Fe(pbpy)(tpy)]+ (Hpbpy=6-phenyl-2,2'-bipyridine and tpy=2,2':6',2''-terpyridine) of this new chromophore class are now reported. Ground-state characterization

  在量子化学计算的基础上，具有富地球金属离子的复杂类[Fe（N ^ N ^ C）（N ^ N ^ N）] +被反复提出作为发色团和潜在的光敏剂。该化合物的母体复合物[Fe（pbpy）（tpy）] +（Hpbpy = 6-苯基-2,2'-联吡啶和tpy = 2,2'：6'，2''-三联吡啶）的合成和光物理性质现在报道了新的生色团类。通过X射线衍射，电化学，光谱电化学，UV / Vis和X射线光谱结合DFT计算对基态进行表征，证明了环金属配体对电子结构的巨大影响。与原型[Fe（tpy）2] 2+配合物相比，光物理性质得到了显着改善。特别是，
• Bis(tridentate) Iron(II) Complexes with a Cyclometalating Unit: Photophysical Property Enhancement with Combinatorial Strong Ligand Field Effect
  作者：Zhou Tang、Xiao-Yong Chang、Qingyun Wan、Jian Wang、Chensheng Ma、Kwok-Chung Law、Yungen Liu、Chi-Ming Che

  DOI：10.1021/acs.organomet.0c00149

  日期：2020.8.10

  reactions of [FeII(C∧Npy∧Npy)Br(PMe3)2] (1, HC∧Npy∧Npy = 6-(phenyl)-2,2′-bipyridine) and [FeII(C∧Nppy∧Nisoquin)Br(PMe3)2] (2, HC∧Nppy∧Nisoquin = 3-(4,6-diphenylpyridin-2-yl)isoquinoline) with tridentate ligands L, affording [FeII(C∧Npy∧Npy)(4′-R-tpy)]+ (3a–e, R = H, Cl, p-ClC6H4, p-MeOC6H4, p-tol, respectively; tpy = 2,2′:6′,2″-terpyridine), [FeII(C∧Nppy∧Nisoquin)(tpy)]+ (4), [FeII(C∧Npy∧Npy)(6-(Ph2PCH2)-bpy)]+

  一系列的双（三齿）环金属oligopyridine络合物的[Fe II（C ∧ Ñ ∧ N）（L）] +已通过的的[Fe的反应合成II（C ∧ Ñ PY ∧ Ñ PY）溴（PME 3）2 ]（1，HC ∧ ñ PY ∧ ñ PY = 6-（苯基）-2,2'-联吡啶）和[铁II（C ∧ ñ PPY ∧ ñ isoquin）溴（PME 3）2 ]（2，HC ∧Ñ PPY ∧ Ñ isoquin = 3-（4,6-二苯基吡啶-2-基）异喹啉）具有三齿配体L，得到的[Fe II（C ∧ Ñ PY ∧ Ñ PY）（4'- R-TPY）] +（图3a - ë，R = H，氯，p -ClC 6 ħ 4，p -MeOC 6 ħ 4，p分别-tol; TPY = 2,2'：6'，2“ -三联吡啶），的[Fe II（ ç ∧ ñ PPY ∧ ñ isoquin）（TPY）] +（4），的[Fe II（C ∧ Ñ
• Hard to Handle: Extremely Labile Hydrido Nickel(II) Complexes of Cyclometalated C^∧N^∧N and N^∧C^∧N Ligands
  作者：Lukas Kletsch、Leo Payen、Antonio Fiorentino、Burgert Blom、Dario Romano、Gerald Hörner、Axel Klein

  DOI：10.1021/acs.organomet.3c00191

  日期：2023.8.28

  the two organonickel(II) scaffolds [Ni(Phbpy)]+ and [Ni(PyPhPy)]+ (HPhbpy = 6-phenyl-2,2′-bipyridine≡HC∧N∧N and Py(HPh)Py = 2,6-di-2-pyridyl-benzene≡N∧(HC)∧N) the hydrido complexes [Ni(C∧N∧N)H] and [Ni(N∧C∧N)H] were studied in a combined experimental/theoretical approach. The hydrido complexes were prepared via the reaction of the halido derivatives [Ni(C∧N∧N)X] and [Ni(N∧C∧N)X] (X = Cl, Br) with Li(Et3BH)

  由两个有机镍 (II) 支架 [Ni(Phbpy)] +和 [Ni(PyPhPy)] + (HPhbpy = 6-苯基-2,2′-联吡啶 ≡HC ∧ N ∧ N 和 Py(HPh)Py = 2 ,6-二-2-吡啶基-苯=N ∧ (HC) ∧ N) 氢配合物[Ni(C ∧ N ∧ N)H] 和[Ni(N ∧ C ∧ N)H] 进行了组合研究实验/理论方法。氢配合物是通过卤代衍生物 [Ni(C ∧ N ∧ N)X] 和 [Ni(N ∧ C ∧ N)X] (X = Cl, Br) 与 Li(Et 3 BH) 反应制备的。超氢化物）。C ∧即使在最低温度下，N ∧ N 络合物也会经历快速还原消除 (RE)，产生 HPhbpy 和 Ni 颗粒，而 PyPhPy 衍生物更稳定。低温1 H 核磁共振 (NMR) 光谱可以检测到 δ = -2.86 ppm 处的信号，该信号可归属于氢配体。不同的稳定性可以直接与碳负离子
• Role of the X Coligands in Cyclometalated [Ni(Phbpy)X] Complexes (HPhbpy = 6-Phenyl-2,2′-bipyridine)
  作者：Nicolas Vogt、Aaron Sandleben、Lukas Kletsch、Sascha Schäfer、Mason T. Chin、David A. Vicic、Gerald Hörner、Axel Klein

  DOI：10.1021/acs.organomet.1c00237

  日期：2021.6.14

  The coligand X was varied in the organonickel complexes [Ni(Phbpy)X] (X = F, Cl, Br, I, C6F5) carrying the anionic tridentate C∧N∧N ligand 6-(phen-2-ide)-2,2′-bipyridine (Phbpy–) to study its effect on electronic structures of these complexes and their activity in Negishi-like C–C cross-coupling catalysis. The complexes were synthesized from the precursor [Ni(COD)2] (COD = 1,5-cyclooctadiene) by chelate-assisted

  携带阴离子三齿 C ∧ N ∧ N 配体 6-(phen-2-ide ) 的有机镍配合物 [Ni(Phbpy)X] (X = F, Cl, Br, I, C 6 F 5 ) 中的共配体X )-2,2'-联吡啶 (Phbpy – ) 研究其对这些配合物的电子结构的影响及其在 Negishi 样 C-C 交叉偶联催化中的活性。该配合物由前体 [Ni(COD) 2]（COD = 1,5-环辛二烯）通过螯合物辅助氧化加成到原配体 6-（2-卤代苯基）-2,2'-联吡啶的苯基 C-X 键中）并以红色粉末形式获得。携带卤化物替代物 X = OMe、OTf（三氟甲磺酸盐）的原配体 X–Phbpy 在该反应中失败。单晶 XRD 使我们能够将 [Ni(Phbpy)Cl] 和 [Ni(Phbpy)I] 的结构添加到先前报道的 Br 衍生物中。循环伏安法显示出对X = C可逆减少6 ˚F 5，氟，氯，而Br和I
• The cyclometalated nickel complex [(Phbpy)NiBr] (Phbpy− = 2,2′-bipyridine-6-phen-2-yl) – Synthesis, spectroscopic and electrochemical studies
  作者：Axel Klein、Benjamin Rausch、Andre Kaiser、Nicolas Vogt、Alexander Krest

  DOI：10.1016/j.jorganchem.2014.10.013

  日期：2014.12

  The new organometallic nickel complex [(Phbpy)NiBr] containing the anionic tridentate N,N,C ligand 6-(phen-2-yl)-2,2'-bipyridine (Phbpy) was synthesised from PhbpyBr and [Ni(COD)(2)] in excellent yields and was fully characterised (MS, NMR, single crystal XRD). [(Phbpy) NiBr] was reacted with (CF3)SiMe3 giving the CF3 complex [(Phbpy)Ni(CF3)]. Both new complexes were studied in detail by electrochemical (CV) and spectroelectrochemical (UV/vis/NIR absorption) methods. For both complexes the first one-electron reduction and the first oxidation of the Br complex occur fully reversible in the CV, while spectroelectrochemistry shows decomposition reactions. The CF3 complex is unstable in solution producing 2-CF3-Phbpy. Reactivity patterns for these reactions were discussed, also in comparison with the non-cyclometalated complex [(bpy)Ni(Mes)Br]. (C) 2014 Elsevier B.V. All rights reserved.