[10-bromo-5,15-diphenylporphyrinato]-magnesium(II) | 193265-35-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: [10-bromo-5,15-diphenylporphyrinato]-magnesium(II)
• 英文别名: (5-bromo-10,20-diphenylporphyrinato)nickel(II)；[5-bromo-10,20-diphenylporphyrinato]nickel(II)；5-bromo-10,20-diphenylporphyrinatonickel(II)
• CAS: 193265-35-9
• 化学式: C₃₂H₁₉BrN₄Ni
• 分子量: 598.124
• InChiKey: FKNGBQZOGSNOBI-TVGBRLMZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.01
• 重原子数：
  38.0
• 可旋转键数：
  2.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  53.98
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  [10-bromo-5,15-diphenylporphyrinato]-magnesium(II) 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.5h， 以68%的产率得到[5-azido-10,20-diphenylporphyrinato]nickel(II)
  参考文献：
  名称：

  Catalyst-Free Aromatic Nucleophilic Substitution of meso-Bromoporphyrins with Azide Anion: Efficient Synthesis and Structural Analyses of meso-Azidoporphyrins

  摘要：

  meso-Mono- or diazidoporphyrins were readily obtained in high yields by the catalyst-free aromatic nucleophilic reaction of the corresponding bromoporphyrins with azide anions under mild conditions. The molecular structures of the obtained azides were unambiguously determined by X-ray crystallographic analysis.

  DOI：

  10.1021/ol202973z
• 作为产物：
  描述：

  [PdBr(10,20-diphenylporphyrinatonickel(II))((R,R)-1,2-bis(methylphenylphosphino)benzene)] 以 氘代氯仿 为溶剂， 生成 [10-bromo-5,15-diphenylporphyrinato]-magnesium(II)
  参考文献：
  名称：

  A new type of chiral porphyrin: Organopalladium porphyrins with chiral chelating diphosphine ligands

  摘要：

  Peripherally palladated Ni(II) porphyrins have been prepared using enantiopure chiral chelating diphosphines as supporting ligands on the attached Pd(II) fragment. Both enantiomers of the following complexes have been obtained in good yields, using oxidative addition of the bromoporphyrin starting material 5-bromo-10,20-diphenylporphyrinatonickel(II) (NiDPPBr (1)) to the [(PdL)-L-0] complex generated in situ from Pd(2)dba(3) and the chiral ligand L [PdBr(NiDPP)(CHIRAPHOS)] (2a,b) [CHIRAPHOS = 2,3-bis(diphenylphosphino)butane], [PdBr(NiDPP)(Tol-BINAP)] (3a,b) [Tol-BINAP) = 2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl] and [PdBr(NiDPP)(diphos)] [diphos = 1, 2-bis(methylphenylphosphino) benzene] (4a,b). The induced asymmetry in the porphyrin was readily detected by H-1 NMR and CD spectroscopy. The porphyrin chiroptical properties are strongly dependent upon the structure of the chiral ligand, such that a monosignate CD signal, and symmetric and asymmetric exciton couplets were observed for 4a, 2b, and 3a,b, respectively. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.10.014

文献信息

• Practical and Efficient Synthesis of Various <i>meso</i>-Functionalized Porphyrins via Simple Ligand-Free Nickel-Catalyzed C−O, C−N, and C−C Cross-Coupling Reactions
  作者：Chao Liu、Dong-Mei Shen、Qing-Yun Chen

  DOI：10.1021/jo0618728

  日期：2007.4.1

  Various meso-functionalized porphyrins were conveniently synthesized by direct reactions of meso-bromoporphyrins with oxygen-, nitrogen-, and carbon-based nucleophiles in moderate to high yields via practical, efficient, and ligand-free nickel-catalyzed C−O, C−N, and C−C bond-forming reactions. The central metal ions of the substrate porphyrin have much effect on the reactions. Introduction of Ni(II)

  通过介孔溴卟啉与氧，氮和碳基亲核试剂的直接反应，可以通过实用，有效且无配体的镍催化的C-O，C-以中等到高的产率方便地合成各种介孔官能化的卟啉N和CC键形成反应。底物卟啉的中心金属离子对反应有很大影响。将Ni（II）作为中心金属离子引入基质卟啉显着加速了交叉偶联。
• Fluoroalkylation of Porphyrins: A Facile Synthesis of Trifluoromethylated Porphyrins by a Palladium-Catalyzed Cross-Coupling Reaction
  作者：Chao Liu、Qing-Yun Chen

  DOI：10.1002/ejoc.200500027

  日期：2005.9

  Various trifluoromethylated porphyrins can be conveniently synthesized in high yields by the reaction of brominated porphyrins with FSO2CF2COOMe/CuI in the presence of catalytic amounts of Pd2(dba)3·CHCl3/AsPh3. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  在催化量的 Pd2(dba)3·CHCl3/AsPh3 存在下，通过溴化卟啉与 FSO2CF2COOMe/CuI 的反应，可以方便地以高产率合成各种三氟甲基化卟啉。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Functionalization of 5,15-Diphenylporphyrin: Preparation and X-Ray Crystal Structures of meso Nitro, Bromo, and Trimethylsilylethynyl Derivatives
  作者：Dennis P. Arnold、Raymond C. Bott、Helen Eldridge、Fiona M. Elms、Graham Smith、Mike Zojaji

  DOI：10.1071/c96193

  日期：——

  Substitutions on 5,15-diphenylporphyrin led to the isolation of mono- and di-bromo and mono- and di-nitro derivatives, which were converted into their respective nickel(II) complexes. Reaction of the bromoporphyrins with iodine/silver nitrite resulted in nitrodebromination as well as conventional nitration. The nickel(II) complex of 5-nitro-10,20-diphenylporphyrin was reduced to the 5-amino derivative. The nickel(II) complexes of the bromoporphyrins were converted into the respective mono- and bis-(trimethylsilylethynyl) species. The crystal structures of 5-nitro-10,20-diphenylporphyrin, 5-bromo- 10,20-diphenylporphyrinatonickel(II), and 10,20-diphenyl-5-(trimethylsilylethynyl)porphyrinatonickel(II) were determined.

  通过对 5,15-二苯基卟啉进行取代，分离出了一溴和二溴以及一硝基和二硝基衍生物。 二溴以及一硝基和二硝基衍生物，并将其转化为各自的 各自的镍(II)络合物。溴卟啉与 碘/亚硝酸银反应，产生硝基脱溴反应和传统的硝化反应。 传统的硝化反应。镍（II）络合物的 5-硝基-10,20-二苯基卟啉的镍(II)络合物被还原成 5-氨基衍生物。这些 溴卟啉的镍(II)络合物被转化为各自的 单(三甲基硅烷基乙炔基)和双(三甲基硅烷基乙炔基)镍(II)络合物。的晶体结构。 的晶体结构。 10,20-二苯基卟啉atonickel(II)和 10,20-二苯基-5-(三甲基硅烷基乙炔基)卟啉atonickel(II)的晶体结构。 测定。
• <i>meso</i>-Porphyrinylphosphine Oxides:  Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric {[10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph₂] and Polymeric Self-Coordinated {[10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph₂]}
  作者：Farzad Atefi、John C. McMurtrie、Peter Turner、Martin Duriska、Dennis P. Arnold

  DOI：10.1021/ic060372u

  日期：2006.8.1

  atom" quencher. The electron-withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterized by multinuclear NMR and UV-visible spectroscopy, as well as mass spectrometry. Single-crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex [NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the

  通过二苯基膦或其氧化物与相应的溴卟啉的钯催化反应，已经制备了在一个或两个内消旋位置被二苯基膦氧化物基团取代的一系列卟啉。分离出化合物MDPP- [P（O）Ph2] n}（M ＝ H 2，Ni，Zn； H 2 DPP ＝ 5，15-二苯基卟啉； n ＝ 1、2），产率为60-95％。据信该反应通过常规的氧化加成，磷酸化和还原消除步骤进行，如eta（1）-palladio（II）卟啉[PdBr（H2DPP）（DPPe）]的化学计量反应（H2DPP = 5,15-具有二苯基膦氧化物的二苯基卟啉； DPPe ＝ 1，2-双（二苯基膦基）乙烷）还产生所需的单卟啉基膦氧化物[H2DPP-P（O）Ph2]。由于对叔膦的极高的空气敏感性，其分离尝试失败。[H2DPP-P（O）Ph2]的可变温度1H NMR研究显示出固有的不对称性，而荧光光谱显示，氧化膦基团不充当“重原子”猝灭剂。通过伏安法证实了氧化膦基
• Peripherally-metallated porphyrins: synthesis and spectra of meso-η1-palladio- and platinioporphyrins and the crystal structures of cis-{PtBr[10,20-diphenylporphyrinatonickel(II)-5-yl](PPh3)2} and trans-{PtBr[10,20-diphenylporphyrin-5-yl](PPh3)2}·0.25CH2Cl2
  作者：Dennis P Arnold、Peter C Healy、Margaret J Hodgson、Michael L Williams

  DOI：10.1016/s0022-328x(00)00185-6

  日期：2000.8

  the PPh3 ligands in 15. The NiDPP ring in 15 suffers ruffling typical of peripherally-crowded Ni(II) porphyrins, the pairs of opposite meso carbons being displaced alternately >±0.4 Å out of the C20N4 mean plane The conformations of the phenyl groups of the PPh3 ligands indicate the presence of non-covalent phenyl–porphyrin π–π interactions. These derivatives are the first isolated examples of peripheral

  一系列的内消旋-η 1 -palladio（II） -和platinio（II）卟啉含有任一单齿15个族配位体（PPH 3，ASPH 3）或螯合二膦（DPPE，DPPP，DPPF）已经准备由氧化加成的单-和5,15-二苯基卟啉（H 2 DPP）的二溴衍生物为Pd（0）和Pt（0）的前体。产物的特征在于1 H-和31 P-NMR，可见光吸收和质谱以及反式-[PtBr（H 2 DPP）（PPh 3）2 ]（14）的X射线晶体结构。0.25CH 2氯2测定了溶剂化物）和顺式-[PtBr（NiDPP）（PPh 3）2 ]（15）。尽管由于15中PPh 3配体的拥挤而存在扭曲，但该结构在Pt原子周围显示出近似方形的平面几何形状。15个位置中的NiDPP环受到周围拥挤的Ni（II）卟啉的典型波动，成对的相对介孔碳在C 20 N 4平均平面之外交替移位>± 0.4ÅPPh 3的苯基构象配体表明存在非共价