[Re(CO)3(5,5′-Me2bipy)(CH3CN)]BF4 | 1236848-42-2

• 英文名称: [Re(CO)3(5,5′-Me2bipy)(CH3CN)]BF4
• 英文别名: [Re(CO)₃(5,5′-Me₂bipy)(CH₃CN)]BF₄；[Re(CO)₃(5,5'-dimethyl-2,2'-bipyridine)(CH₃CN)]BF₄；[fac-Re(5,5'-dimethyl-2,2'-bipyridine)(CO)₃(MeCN)]BF₄；[fac-Re(5,5'-Me₂bpy)(CO)₃(MeCN)]BF₄；fac-[renium(I)(tricarbonyl)(5,5'-dimethyl-2,2'-bipyrdine)(acetonitrile)](tetrafluoroborate)；fac-[Re(CO)3(5,5'-dimethyl-2,2'-bipyridine)(acetonitrile)]BF4；fac-[Re(CO)3(acetonitrile)(5,5'-dimethyl-2,2'-bipyridine)]BF4
• CAS: 1236848-42-2
• 化学式: BF₄*C₁₇H₁₅N₃O₃Re
• 分子量: 582.336
• InChiKey: RRJTXMVJYNTWQI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  5 5'-二甲基-2,2'-二吡啶 、 [Re(CO)3(5,5′-Me2bipy)(CH3CN)]BF4 反应 4.0h， 以65%的产率得到[cis-Re(5,5'-dimethyl-2,2'-bipyridine)₂(CO)₂]BF₄
  参考文献：
  名称：

  im（I）二亚胺二羰基化合物的光物理和超快过程。

  摘要：

  在这项工作中，一系列九种通式为顺式-[Re（N ^ N）2（CO）2 ] +的Re（I）二亚胺二羰基配合物（N ^ N是各种2,2'-联吡啶（bpy）或1,10-菲咯啉（phen）衍生物）并进行光谱研究以系统地评估驻留在二亚胺配体上的各种取代基的光物理结果。这些全色吸收发色团经过结构表征，评估了它们的电化学和光谱电化学性质，并使用了静态和动态电子吸收，光致发光（PL）和红外光谱从超快到超纳秒的时间范围进行了研究。电子结构计算进一步支持了超快时间分辨红外（TRIR）分析，该计算表征了两个C内的变化金属-配体电荷转移（MLCT）激发态形成时的O振动模式。这一系列二羰基分子的MLCT激发态衰变似乎与能隙定律行为完全一致，其中非辐射衰变速率常数随激发态-基态能量分离的降低呈对数增加，除非预期的取代基是苯基或叔叔丁基。

  DOI：

  10.1039/d0dt01765e
• 作为产物：
  描述：

  fac-[Re(CO)3(MeCN)3]BF4 以 not given 为溶剂， 生成 [Re(CO)3(5,5′-Me2bipy)(CH3CN)]BF4
  参考文献：
  名称：

  Superbasic Amidine Monodentate Ligands in fac-[Re(CO)₃(5,5′-Me₂bipy)(Amidine)]BF₄ Complexes: Dependence of Amidine Configuration on the Remote Nitrogen Substituents

  摘要：

  Addition of various RNH2 to fac-[Re(CO)(3)(5,5'-Me(2)bipy)(CH3CN)]BF4 (1) converts the acetonitrile ligand to the amidine ligand (a superbase) in fac[Re(CO)3(5,5'-Me(2)bipy)(HNC(CH3)NHR)]BF4 products. Each complex has four conceivable isomers (E, E', Z, and Z') because the amidine CN bonds have double-bond character, and the two remote NHR group substituents are different. The reaction of 1 in acetonitrile is complete in 6 to 96 h (25 degrees C) and forms fac[Re(CO)(3)(5,5'-Me(2)bipy)(HNC(CH3)NHR)]BF4 E' and Z isomers. Only the E' isomer formed crystals (R = methyl, isopropyl, isobutyl, tert-butyl, and benzyl). Upon dissolution of such crystals in acetonitrile-d(3), NMR spectra with highly dominant E' signals gradually changed (similar to 15 mm at room temperature) to spectra with signals for an equilibrium mixture of E' and Z isomers. Such slow E'-to-Zisomer interchange is also indicated by 2D ROESY NMR data used primarily to assign solution structure. Equilibrium ratios (E':Z) of similar to 65:35 for R = methyl, isopropyl, and isobutyl and 83:17 for R = tert-butyl demonstrate that increasing the remote NHR group steric bulk above a threshold size favors the E isomer. Consistent with this trend, fac-[Re(CO)(3)(5,5'-Me(2)bipy)(HNC(CH3)NH2)BF4, with a remote NH2 (low bulk) group, favors the Z isomer. In contrast, although the remote NH(benzyl) group in fac-[Re(CO)(3)(5,5'-Me(2)bipy)(HNC(CH3)NH(CH2C6H5)BF4 has only moderate bulk, the E isomer has high abundance as a result of favorable 5,5'-Me(2)bipy/benzyl stacking, evidence for which is present in both solid and solution states. The fac-[Re(CO)(3)(5,5'-Me(2)bipy)(HNC(CH3)NHR)]BF4 E isomer can be detected in solvents of low polarity. However, the Z isomer was not observed, undoubtedly because unfavorable remote-group clashes with the equatorial ligands destabilize this isomer. Challenge studies with a 5-fold excess of 4-dimethylaminopyridine in acetonitrile-d(3) establish that fac[Re(CO)(3)(5,5'-Me(2)bipy)(HNC(CH3)NHCH(CH3)(2)]BF4 is robust because the isopropylamidine ligand was not displaced, consistent with the superbase character of amidine ligands.

  DOI：

  10.1021/ic100714m

文献信息

• New Monodentate Amidine Superbasic Ligands with a Single Configuration in <i>fac</i>-[Re(CO)₃(5,5′- or 6,6′-Me₂bipyridine)(amidine)]BF₄ Complexes
  作者：Pramuditha Abhayawardhana、Patricia A. Marzilli、Theshini Perera、Frank R. Fronczek、Luigi G. Marzilli

  DOI：10.1021/ic300625n

  日期：2012.7.2

  C2-symmetrical saturated heterocyclic amines yielded 10 new amidine complexes, fac-[Re(CO)3(L)(HNC(CH3)N(CH2CH2)2Y)]BF4 [Y = CH2, (CH2)2, (CH2)3, NH, or O]. All 10 complexes possess the novel feature of having only one isomer (amidine E configuration), as established by crystallographic and 1H NMR spectroscopic methods. We are confident that NMR signals of the other possible isomer (amidine Z configuration)

  处理两种前体fac -[Re(CO) 3 (L)(CH 3 CN)]BF 4 [L = 5,5'-二甲基-2,2'-联吡啶 (5,5'-Me 2 bipy) ( 1 ) 和 6,6'-二甲基-2,2'-联吡啶 (6,6'-Me 2 bipy) ( 2 )] 与 5 个C 2对称饱和杂环胺生成 10 个新的脒络合物，fac -[ Re(CO) 3 (L)(HNC(CH 3 )N(CH 2 CH 2 ) 2 Y)]BF 4 [Y = CH 2、(CH 2 ) 2、(CH 2 ) 3、NH 或 O] 。通过晶体学和1 H NMR 光谱方法确定，所有 10 种配合物都具有仅具有一种异构体（脒E构型）的新特征。我们确信，如果存在其他可能的异构体（脒Z构型）的 NMR 信号，也会被检测到。在密切相关的脒络合物中很容易检测到异构体，因为脒 C-N3 键的双键特征（N3 与 Re 结合）导致E到Z异构体的互换缓慢。新的fac
• Iminoether Complexes of the Type, <i>fac</i> ‐[Re(CO) ₃ L{HNC(CH ₃ )OCH ₃ }]BF ₄ (L = Bipyridine or a Substituted Bipyridine): Synthesis and Properties
  作者：Theshini Perera、Pramuditha Abhayawardhana、Frank R. Fronczek、Patricia A. Marzilli、Luigi G. Marzilli

  DOI：10.1002/ejic.201100768

  日期：2012.2

  (an iminoether) complexes, fac-[Re(CO)3LHNC(CH3)OCH3}]BF4 [where L = 2,2′-bipyridine (bipy), 4,4′-Me2bipy, 5,5′-Me2bipy, or 6,6′-Me2bipy], were formed when fac-[Re(CO)3(CH3CN)3]BF4 in acetonitrile/methanol was treated with 2,2′-bipyridine (bipy) or the dimethyl-2,2′-bipyridines (4,4′-Me2bipy, 5,5′-Me2bipy, or 6,6′-Me2bipy). Structural analysis of the four fac-[Re(CO)3LHNC(CH3)OCH3}]BF4 complexes revealed

  乙酰亚胺酸甲酯（一种亚氨基醚）配合物 fac-[Re(CO)3LHNC(CH3)O }]BF4 [其中 L = 2,2'-联吡啶 (bipy), 4,4'-Me2bipy, 5,5 '-Me2bipy，或 6,6'-Me2bipy]，是在乙腈/甲醇中的 fac-[Re(CO)3( CN)3]BF4 用 2,2'-联吡啶 (bipy) 或二甲基- 2,2'-联吡啶（4,4'-Me2bipy、5,5'-Me2bipy 或 6,6'-Me2bipy）。四种 fac-[Re(CO)3LHNC( )O }]BF4 复合物的结构分析表明，所有复合物都与 Z 构型中的亚胺醚配体结晶，并且 L 中涉及两个吡啶环的畸变是除了 6,6'-Me2bipy 高度扭曲外，其他都是次要的。6,6'-Me2bipy 配体的这种畸变反映在 NMR 光谱数据中。复合物形成后，6,6'-Me2bipy 的
• Models for B₁₂-Conjugated Radiopharmaceuticals. Cobaloxime Binding to New <i>fac</i>-[Re(CO)₃(Me₂Bipyridine)(amidine)]BF₄ Complexes Having an Exposed Pyridyl Nitrogen
  作者：Nerissa A. Lewis、Patricia A. Marzilli、Frank R. Fronczek、Luigi G. Marzilli

  DOI：10.1021/ic5016675

  日期：2014.10.20

  pyridine) complexes increased with increasing basicity of the 4-Xpy derivative, a finding attributed to the influence of the magnetic anisotropy of the cobalt center on the shifts of the 1H NMR signals of the pyridyl protons closest to Co. Our method of employing a coordinate bond for conjugating the fac-[ReI(CO)3] core to a vitamin B12 model could be extended to natural B12 derivatives. Because B12 compounds

  新的单核am络合物FAc- [Re（CO）3（Me 2 bipy）（HNC（CH 3）（pyppz））] BF 4 [（4,4'-Me 2 bipy（1），5,5'-通过处理母体FAc- [Re I（CO）3（Me 2 bipy ），合成了Me 2 bipy（2）和6,6'-Me 2 bipy（3）]（bipy = 2,2'-bipyridine））（CH 3 CN）] BF 4与C 2的络合物-对称胺1-（4-吡啶基）哌嗪（pyppzH）。轴向am配体具有暴露的高碱性吡啶基氮。复合物的反应1 - 3用B 12模型，（PY）的Co（DH）2 Cl（上DH =二甲基乙二肟的单价阴离子），在CH 2氯2，得到相应的双核配合物，即，FAC - [的Re（CO）3（Me 2 bipy）（μ-（HNC（CH 3）（pyppz）））Co（DH）2 Cl] BF 4 [（4,4'-Me 2 bipy（4），5