9,9'-bis<4,5-diazafluorene> | 67664-24-8

• 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: 9,9'-bis<4,5-diazafluorene>
• 英文别名: 9,9′-bis(4,5-diazafluorenyl)；9,9'-bis(4,5-diaza-9H-fluorene)；9,9'-bis-4,5-diaza-9H-fluorenyl；9,9'-bis(4,5-diazafluorene)；5H,5'H-[5,5']bi[cyclopenta[2,1-b;3,4-b']dipyridinyl]；8-(3,13-Diazatricyclo[7.4.0.02,7]trideca-1(9),2(7),3,5,10,12-hexaen-8-yl)-3,13-diazatricyclo[7.4.0.02,7]trideca-1(9),2(7),3,5,10,12-hexaene
• CAS: 67664-24-8
• 化学式: C₂₂H₁₄N₄
• 分子量: 334.38
• InChiKey: ZQXQAKMRDVIPFV-UHFFFAOYSA-N

物化性质

• 熔点：
  317-320 °C (decomp)(Solv: methanol (67-56-1))
• 沸点：
  529.4±45.0 °C(Predicted)
• 密度：
  1.374±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  26
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  9,9'-bis<4,5-diazafluorene> 在 过氧化苯甲酰 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 7.0h， 生成 9,9'-bi-4,5-diazafluorenylidene-7,7,8,8-tetracyanoquinodimethane complex
  参考文献：
  名称：

  Synthesis, Structure and Chemistry of a Twisted Olefinic Bis-didentate Proligand: 5,5′-Bi-5H-cyclopenta[2,1-b : 3,4-b′]dipyridinylidene

  摘要：

  The elusive chiral twisted alkene, 5,5'-bi-5H-cyclopenta[2.1-b : 3,4-b']dipyridinylidene, known also as 9,9'-bi-4,5-diazafluorenylidene (BDAF), has been prepared in racemic form from 9-bromo-4,5-diazafluorene and from 9,9'-bi-4,5-diazafluorenyl and fully characterised. X-Ray measurements show that there is a twist of 37.8 degrees about the double bond between the 4,5-diazafluorenylidene units. A 1:1 charge-transfer compound with 7,7,8,8-tetracyanoquinodimethane (TCNQ) contains an unusual packing arrangement which is centred around the formation of spiral stacks. Each BDAF molecule contributes one 4,5-diazofluorenylidene unit to the backbone of the stack, while the second half is involved in hydrogen-bonding interactions and additional stacking with TCNQ. Examples of complexes containing the axially symmetric tetradentate ligand binding to one and to two metal ions. [M(bdaf)Cl-2] and [(MCl2)(2)(bdaf)] (M = Co, Ni, Zn), are reported.

  DOI：

  10.1002/(sici)1522-2675(19991006)82:10<1666::aid-hlca1666>3.0.co;2-k
• 作为产物：
  描述：

  5,5'-hydrazine-1,2-diylidene-bis(5H-pyrido[3',2':4,5]cyclopenta[1,2-b]pyridine) 、 肼 以39%的产率得到
  参考文献：
  名称：

  MLOCHOWSKI, J.;SZULC, Z., POL. J. CHEM., 1983, 57, N 1-3, 33-39

  摘要：

  DOI：

文献信息

• Transfer hydrogenation of aryl ketones with homogeneous ruthenium catalysts containing diazafluorene ligands
  作者：Mehmet Fırat Baran、Feyyaz Durap、Murat Aydemir、Akın Baysal

  DOI：10.1002/aoc.3538

  日期：2016.12

  Novel cationic ruthenium(II) complexes bearing a 4,5‐diazafluorene unit and p‐cymene as ligands have been synthesised. The complexes were characterised based on elemental analysis and Fourier transform infrared and nuclear magnetic resonance spectroscopies. The synthesised Ru(II) complexes were employed as pre‐catalysts for the transfer hydrogenation of aromatic ketones using 2‐propanol as both hydrogen

  合成了带有4,5-二氮杂芴单元和对苯异丙基作为配体的新型阳离子钌（II）配合物。根据元素分析，傅立叶变换红外光谱和核磁共振光谱对复合物进行表征。合成的Ru（II）配合物被用作在NaOH存在下使用2-丙醇作为氢源和溶剂的芳香酮转移加氢的预催化剂。在将取代的苯乙酮还原为相应的仲醇中，所有络合物均显示出高催化剂催化活性。获得的催化产物的转化率为80-99％。在所研究的七个新配合物中，最有效的催化剂的周转频率为255–291 h -1分别对应于85％到97％的转化率。版权所有©2016 John Wiley＆Sons，Ltd.
• Solvent and Counter‐Ion Induced Coordination Environment Changes Towards Ag ^I Coordination Polymers
  作者：Arvind Kumar Gupta、Daniel Morales Salazar、Andreas Orthaber

  DOI：10.1002/ejic.201900722

  日期：2019.9.8

  A series of silver coordination polymers based on the 9,9 '-bis(4,5-diazafluorene) (BDF-H-2) ligand is presented. The choice of counterions and reaction conditions dictate the observed topology on ...

  介绍了一系列基于 9,9'-双 (4,5-二氮杂芴) (BDF-H-2) 配体的银配位聚合物。反离子和反应条件的选择决定了观察到的拓扑结构...
• 5,5?-Bi-5H-cyclopenta[2,1-b;3,4-b?]dipridinylidene, a New Bridging Ligand for Metal Complexes. Preliminary Communication
  作者：Marianne Riklin、Alex von Zelewsky

  DOI：10.1002/hlca.19960790812

  日期：1996.12.11

  5,5′-Bi-5H-cyclopenta[2,1-b;3,4-b′]dipyridinylidene(1) was synthesized in three steps from 9,10-phenanthroline and characterized by UV/VIS and NMR spectroscopy, mass spectrometry, and cyclic voltammetry. Its ability to act as a bridging ligand is demonstrated by the synthesis of the complexes [Ru(bpy)2(1)](PF6)2 (6) and [Ru(bpy)2}2(1)](PF6)4 (7) (bpy = 2,2′-bipyridine).

  由9,10-菲咯啉经三个步骤合成了5,5'-Bi-5 H-环戊基[2,1- b ; 3,4- b ']二吡啶亚基（1），并通过UV / VIS和NMR谱进行了表征，质谱和循环伏安法。配合物[Ru（bpy）2（1）]（PF 6）2（6）和[Ru（bpy）2 } 2（1）]（PF 6）4（7）（bpy = 2,2'-联吡啶）。
• Thermal Dihydrogen Elimination from Cp*₂Yb(4,5-diazafluorene)
  作者：Grégory Nocton、Corwin H. Booth、Laurent Maron、Richard A. Andersen

  DOI：10.1021/om300876b

  日期：2013.3.11

  The reaction of 4,5-diazafluorene with Cp-2*Yb(OEt2), where Cp* is pentamethylcyclopentadienyl, affords the isolable adduct Cp-2*Yb(4,5-diazafluorene) (1), which slowly eliminates H-2 to form Cp-2*Yb(4,5-diazafluorenyl) (2); the net reaction is therefore 1 --> 2 + H-center dot. The ytterbium atom in 1 is shown to be intermediate valent by variable-temperature L-III-edge X-ray absorption near edge (XANES) spectroscopy, consistent with its low effective magnetic moment (mu(eff)). The experimental studies are supported by complete active space self-consistent field (CASSCF) calculations, showing that two open-shell singlets he below the triplet state. The two open shell singlets are calculated to be multiconfigurational and closely spaced, in agreement with the observed temperature dependence of the XANES and chi data, which are fit to a Boltzmann distribution. A mechanism for dihydrogen formation is proposed on the basis of kinetic and labeling studies to involve the bimetallic complex (Cp-2*Yb)(2)(4,5-diazafluorenyl)(2), in which the heterocyclic amine ligands are joined by a carbon-carbon bond at C(9)-C(9').
• Mlochowski, Jacek; Szulc, Zdzislaw, Polish Journal of Chemistry, 1983, vol. 57, # 1/3, p. 33 - 39
  作者：Mlochowski, Jacek、Szulc, Zdzislaw

  DOI：——

  日期：——