fac-[Re(CO)3(MeCN)3]BF4 | 75576-70-4

• 英文名称: fac-[Re(CO)3(MeCN)3]BF4
• 英文别名: fac-[Re(CO)3(NCMe)3]BF4；fac-[Re(CO)3(acetonitrile)3]BF4；fac-[renium(I)(carbonyl)3(acetonitrile)3](tetrafluoroborate)；fac-[Re(CO)3(CH3CN)3]BF4
• CAS: 75576-70-4
• 化学式: BF₄*C₉H₉N₃O₃Re
• 分子量: 480.2
• InChiKey: ASLKUHAEFGYNOR-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：

  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
• 作为产物：
  描述：

  、 乙腈 以 乙腈 为溶剂， 以85%的产率得到fac-[Re(CO)3(MeCN)3]BF4
  参考文献：
  名称：

  Reaction of [Re(CO)6]+ cation with cyclopentadienylthallium derivatives. Formation of cyclopentadienylrheniumtricarbonyl derivatives via [Re(CO)3L3]+ (L=solvent)

  摘要：

  The reaction of [Re(CO)(6)](+) with cyclopentadienylthallium derivatives in DMSO or in DMF affords the corresponding cyclopentadienyltricarbonylrhenium derivatives with high yields. The cyclopentadienyl transfer from CpTl to [Re(CO)(6)][BF4] was also carried out in acetonitrile. However, in this case it is necessary to work in a sealed tube heated at 160 degreesC. Two compounds are obtained: the expected CpRe(CO)(3) and a rhenium salt which was identified as [Re(CO)(3)(CH3CN)(3)][BF4]. The triacetonitrile tricarbonyl cation fac-[Re(CO)(3)(CH3CN)(3)](+) is also formed upon dissolution of [Re(CO)(6)][BF4] in acetonitrile and heating at 160 degreesC under pressure. It reacts afterwards with CpTl in acetonitrile to yield CpRe(CO)(3) (32%). Thus, [Re(CO)(3)(CH3CN)(3)][BF4] can be considered as an intermediate for this ligand-transfer reaction. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00110-5

文献信息

• Bimetallic complexes
  作者：Thomas Gutmann、Eberhard Dombrowski、Nicolai Burzlaff、Wolfdieter A. Schenk

  DOI：10.1016/s0022-328x(97)00583-4

  日期：1998.2

  including an X-ray crystal structure determination of the CDCl3 solvate (triclinic, space group P (No. 2), a=945.1(5) pm, b=1113.9(6) pm, c=1888.5(10) pm, α=92.36(3)°, β=89.98(3)°, γ=113.49(2)°, V=1.821(2)×109 pm3, Z=2). 1 and the highly reactive `salt' [Re(CO)5FBF3] give the mono-bridged ionic complex [Cp′Cl2Zr(μ-Cp′)Re(CO)5]BF4 (3). The doubly Cp′-bridged complex [Cp′2Cl2ZrReCl(CO)3] (4) may be obtained

  双金属Zr的Re配合物与桥接Ç 5 ħ 4 PPH 2配体（以下简称为CP'）是从单核二氯二茂锆的CP可访问的“ 2的ZrCl 2（1）和反应铼配合物。尝试从1和[Re（CO）3（NCMe）3 ] BF 4合成阳离子络合物导致形成无锆化合物[ReCl（CO）3（C 10 H 10（PPh 2）2） ]（2）。2个显然是由CP'-Zr键断裂，随后分子内Diels-Alder加成形成的。对该化合物进行了全面表征，包括确定CDCl 3溶剂化物的X射线晶体结构（三斜晶系，空间群P （第2号），a = 945.1（5）pm，b = 1113.9（6）pm，c = 1888.5（ 10）pm，α = 92.36（3）°，β = 89.98（3）°，γ = 113.49（2）°，V = 1.821（2）×10 9 pm 3，Z = 2）。1和高反应性的“盐” [Re（CO）5 FBF 3 ]得到单桥离子复合物[CP'Cl
• Fluorescent Rhenium-Naphthalimide Conjugates as Cellular Imaging Agents
  作者：Emily E. Langdon-Jones、Nadine O. Symonds、Sara E. Yates、Anthony J. Hayes、David Lloyd、Rebecca Williams、Simon J. Coles、Peter N. Horton、Simon J.A. Pope

  DOI：10.1021/ic500142z

  日期：2014.4.7

  diethylene glycol (L3), and benzyl alcohol (L4) variants. The species are fluorescent in the visible region between 505 and 537 nm through a naphthalimide-localized intramolecular charge transfer, with corresponding fluorescent lifetimes of up to 9.8 ns. The ligands and complexes were investigated for their potential as imaging agents for human osteoarthritic cells and protistan fish parasite Spironucleus

  已经基于f fac-三羰基核合成了一系列生物相容的荧光rh-萘二甲酰亚胺共轭物。荧光配体基于N-官能化的4-氨基衍生的1,8-萘二甲酰亚胺核心，并结合了二烯丙基胺结合单元以螯合Re（I）；结构上的变化符合具有乙基甘氨酸酯（L 1），3-丙醇（L 2），二甘醇（L 3）和苯甲醇（L 4）的烷基化酰亚胺的性质。）变体。该物种通过萘二甲酰亚胺定位的分子内电荷转移在505至537 nm的可见光区域内发出荧光，相应的荧光寿命高达9.8 ns。使用共聚焦荧光显微镜研究了配体和配合物作为人类骨关节炎细胞和原生鱼寄生虫螺旋体涡虫成像剂的潜能。结果表明，萘二甲酰亚胺结构的特定性质用于控制这些成像剂的摄取和细胞内定位。观察到游离配体和复合物之间的显着差异，L 2的Re（I）复合物在S. vortens中显示出氢核糖体定位。
• 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
• Formation of a Metal-to-Nitrogen Bond of Normal Length by a Neutral Sufonamide Group within a Tridentate Ligand. A New Approach to Radiopharmaceutical Bioconjugation
  作者：Theshini Perera、Pramuditha Abhayawardhana、Patricia A. Marzilli、Frank R. Fronczek、Luigi G. Marzilli

  DOI：10.1021/ic302180t

  日期：2013.3.4

  tertiary sulfonamide group, N(SO2R)R′2, can rehybridize to form a M–N bond of normal length even when the group is in a linear tridentate ligand, such as in the new tridentate N(SO2R)dpa ligands derived from di-(2-picolyl)amine (N(H)dpa). N(SO2R)dpa ligands were used to prepare fac-[Re(CO)3(N(SO2R)dpa)](PF6 or BF4) complexes. Structural characterization of the new complexes established that the tertiary

  我们证明叔磺酰胺基团N (SO 2 R)R' 2可以再杂交形成正常长度的 M-N 键，即使该基团处于线性三齿配体中，例如在新的三齿N (SO 2 R)dpa 配体衍生自二-(2-甲基吡啶)胺 ( N (H)dpa)。N (SO 2 R)dpa 配体用于制备fac -[Re(CO) 3 ( N (SO 2 R)dpa)](PF 6或 BF 4) 复合体。新复合物的结构表征确定叔磺酰胺氮原子与 Re 结合，伴随 sp 2 -sp 3再杂交，促进面部协调。新的fac -[Re(CO) 3 ( N (SO 2 R)dpa)]X 结构为任何金属提供了唯一的例子，其中磺酰胺作为非环状线性三齿配体的一部分和正常的金属 - 氮（叔磺酰胺）键长。以前罕见的这种正常 M-N 键的例子只在更受限制的情况下被发现，例如三足四齿配体。我们对新三齿N (SO 2R)dpa 配体将开发与fac -[M I (CO) 3