fac-[Re(H₂O)₃(CO)₃]Br | 828915-71-5

• 英文名称: fac-[Re(H₂O)₃(CO)₃]Br
• 英文别名: fac-[Re(CO)₃(H₂O)₃]Br
• CAS: 828915-71-5
• 化学式: Br*C₃H₆O₆Re
• 分子量: 404.188
• InChiKey: JIBPYULGGIAOQC-UHFFFAOYSA-M

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(H₂O)₃(CO)₃]Br 以 正己烷 、 乙酸乙酯 为溶剂， 生成 tetra[(μ-hydroxy)tricarbonylrhenium(I)] tetrahydrate
  参考文献：
  名称：

  [Re(CO)3(H2O)3]Br 的便捷合成、化学表征和反应性：[Re(CO)3(CH3CN)2Br] 的晶体和分子结构

  摘要：

  摘要 有用的合成前体 [Re(CO)3(H2O)3]Br (1) 可以通过将 [Re(CO)5]Br 在 H2O 中回流 24 小时以接近定量的产率制备。浓缩溶液后，化合物 1 被分离为微晶浅绿色粉末，可溶于水和极性有机溶剂。从甲醇中重结晶得到 [Re(CO)3(MeOH)2Br] (2)，而从乙腈中重结晶得到结晶 [Re(CO)3(CH3CN)2Br](3)。1 的水配体的不稳定性也表现在从乙酸乙酯/己烷重结晶时，产生 [Re(CO)3(OH)]4·4H2O (4·4H2O)。将 1 与联吡啶胺的反应化学与常规起始材料 [NEt4]2[Re(CO)3Br3] 的反应化学进行了比较，结果表明可生成单相化合物，没有被 NEt4Br 污染。晶体数据：C7H6BrN2O3Re (3)：正交 Pnma, a = 6.2289(3) A, b = 13.1323(7) A, c = 13.1700(7)

  DOI：

  10.1016/j.inoche.2004.07.006
• 作为产物：
  描述：

  五羰基溴铼(I) 、 水 以 水 为溶剂， 以99%的产率得到fac-[Re(H₂O)₃(CO)₃]Br
  参考文献：
  名称：

  [Re(CO)3(H2O)3]Br 的便捷合成、化学表征和反应性：[Re(CO)3(CH3CN)2Br] 的晶体和分子结构

  摘要：

  摘要 有用的合成前体 [Re(CO)3(H2O)3]Br (1) 可以通过将 [Re(CO)5]Br 在 H2O 中回流 24 小时以接近定量的产率制备。浓缩溶液后，化合物 1 被分离为微晶浅绿色粉末，可溶于水和极性有机溶剂。从甲醇中重结晶得到 [Re(CO)3(MeOH)2Br] (2)，而从乙腈中重结晶得到结晶 [Re(CO)3(CH3CN)2Br](3)。1 的水配体的不稳定性也表现在从乙酸乙酯/己烷重结晶时，产生 [Re(CO)3(OH)]4·4H2O (4·4H2O)。将 1 与联吡啶胺的反应化学与常规起始材料 [NEt4]2[Re(CO)3Br3] 的反应化学进行了比较，结果表明可生成单相化合物，没有被 NEt4Br 污染。晶体数据：C7H6BrN2O3Re (3)：正交 Pnma, a = 6.2289(3) A, b = 13.1323(7) A, c = 13.1700(7)

  DOI：

  10.1016/j.inoche.2004.07.006

文献信息

• Rhenium Complexes Based on an N ₂ O Tridentate Click Scaffold: From Synthesis, Structural and Theoretical Characterization to a Radiolabelling Study
  作者：Romain Eychenne、Sihem Guizani、Jin‐Hui Wang、Claude Picard、Nadia Malek、Paul‐Louis Fabre、Mariusz Wolff、Barbara Machura、Nathalie Saffon、Nicolas Lepareur、Eric Benoist

  DOI：10.1002/ejic.201600877

  日期：2017.1.3

  A general synthetic approach for a novel range of semi-rigid bifunctional chelating agents (BCAs) including an aromatic ring and a triazolyl moiety in the chelating unit, for the fac-[M(CO)3]+ core (M = 185/187Re or 188Re) was investigated. The strategy included the facile preparation of these N2O ligands bearing various functionalized arms (carboxylate, terminal alkyne, aromatic amine…). The reaction

  一系列新型半刚性双功能螯合剂 (BCA) 的通用合成方法，包括芳环和螯合单元中的三唑基部分，用于 fac-[M(CO)3]+ 核 (M = 185/187Re或 188Re) 进行了研究。该策略包括轻松制备这些带有各种功能化臂（羧酸盐、末端炔烃、芳香胺……）的 N2O 配体。商业 [Re(CO)5Cl]（或新制备的 [Re(H2O)3(CO)3]Brprecursor）与我们的 BCA 在甲醇中的反应导致形成稳定的中性三羰基铼配合物，通式为 [Re(CO) 3(L)] (LH = 5, 10, 11)，收率高。这些化合物的特征在于化合物 [Re(CO)3(5)] 和 [Re(CO)3(11)] 的红外、质谱、核磁共振、电化学、X 射线晶体学以及 DFT 计算。类似的铼-188 配合物 [188Re(CO)3(5)] 和 [188Re(CO)3(11)] 也通过 5 或 11 与 fac-[188Re
• A functionalized heterobimetallic^99mTc/Re complex as a potential dual-modality imaging probe: synthesis, photophysical properties, cytotoxicity and cellular imaging investigations
  作者：Alison François、Céline Auzanneau、Valérie Le Morvan、Chantal Galaup、Hannah S. Godfrey、Louise Marty、Alexandre Boulay、Marine Artigau、Béatrice Mestre-Voegtlé、Nadine Leygue、Claude Picard、Yvon Coulais、Jacques Robert、Eric Benoist

  DOI：10.1039/c3dt51968f

  日期：——

  A novel bimodal fluorescent/radiolabelled probe based on a pyridyltriazole scaffold (known as pyta) is reported here. The final dual imaging agent combines carboxylate functionalization, for biomolecule conjugation, with two distinct metal chelating sites: a pyta-based tricarbonylrhenium moiety as a fluorescent probe and a 99mTc(CO3)+ core through the tridentate chelating iminodiacetic acid (IDA) clamp as a SPECT reporter. The heterodinuclear 99mTc/Re complex 8, as well as its non-radioactive dirhenium analog 7, was prepared in six steps. The 99mTc/Re agent is water-soluble and stable against histidine challenge. Its structural characterization was achieved by HPLC comparison with the non-radioactive complex 7. Upon excitation in the MLCT band at 321 nm, the compound 7 exhibits a bright green luminescence centered at 496 nm, with a quantum yield of 0.86% in Tris buffer, pH 7.4. Additionally, the influence of this compound on cell viability was tested on malignant cell lines (A549, HT29 and MCF-7 human lung, colon and breast carcinomas, respectively). Cell viability after 72 h incubation at 37 °C with 300 μmol of complex 7 was >60% for all cell lines. Finally, cellular uptake studies of compound 7 were performed by fluorescent microscopy, showing that the complex was clearly detected at the cellular level in A549 cells and to a lesser extent in HT29 cells. Taking into consideration the luminescent properties, the good radiochemical purity and the promising biological data (in vitro stability, non-toxicity, and cell tracking in two cell lines), the functionalized 99mTc/Re dinuclear compound 8 can be considered a potential pre- and intraoperative diagnostic probe.

  本文报道了一种基于吡啶基三唑骨架（称为pyta）的新型双模态荧光/放射性标记探针。最终的双重成像试剂结合了羧酸盐功能化（用于生物分子缀合）和两种不同的金属螯合位点：基于pyta的三羰基铼部分作为荧光探针，以及通过三齿螯合的亚氨基二乙酸（IDA）夹钳的99mTc(CO3)+核心作为SPECT报告器。异双核99mTc/Re配合物8及其非放射性双铼类似物7在六步反应中制备。99mTc/Re试剂水溶性良好且对组氨酸具有稳定性。其结构表征通过高效液相色谱与非放射性配合物7进行比较实现。在321 nm的MLCT带激发下，化合物7在496 nm处显示出明亮的绿色发光，在Tris缓冲液（pH 7.4）中的量子产率为0.86%。此外，在恶性细胞系（分别是人肺A549、结肠HT29和乳腺癌MCF-7）上测试了该化合物对细胞活力的影响。在37°C下与300 μmol的配合物7共同孵育72小时后，所有细胞系的细胞活力均>60%。最后，通过荧光显微镜进行了化合物7的细胞摄取研究，显示该配合物在A549细胞中清晰可见，在HT29细胞中程度较小。考虑到其发光特性、良好的放射化学纯度和有前景的生物数据（体外稳定性、无毒性以及在两种细胞系中的细胞追踪），功能化的99mTc/Re双核化合物8可被视为潜在的术前和术中诊断探针。
• ^99m Tc ^I /Re ^I Tricarbonyl Complexes with Tridentate Cysteamine Based Ligands: Synthesis, Characterization and in vitro/in vivo Evaluation
  作者：Carolina Moura、Lurdes Gano、Isabel C. Santos、Isabel Santos、António Paulo

  DOI：10.1002/ejic.201100796

  日期：2011.12

  Tricarbonyl MI (M = Re, 99mTc) complexes of a new tridentate cysteamine based chelator have been synthesized and fully characterized. To gain an insight into the usefulness of this new chelator for labeling biomolecules with a fac-[M(CO)3]+ core, the ligand framework has been functionalized with a N-(dialkylaminoalkyl) pharmacophore. The corresponding 99mTcI complexes showed moderate affinity for melanin

  基于三齿半胱胺的新型螯合剂的三羰基 MI (M = Re, 99mTc) 复合物已被合成并充分表征。为了深入了解这种新型螯合剂在标记具有 fac-[M(CO)3]+ 核心的生物分子方面的有用性，配体框架已用 N-（二烷基氨基烷基）药效团进行了功能化。相应的 99mTcI 复合物显示出对黑色素的中等亲和力和 B16F1 鼠黑色素瘤细胞对细胞的中等吸收，因此值得在体内进一步评估作为检测黑色素瘤的放射性探针。
• Syntheses of bifunctional 2,3-diamino propionic acid-based chelators as small and strong tripod ligands for the labelling of biomolecules with 99mTc
  作者：Yu Liu、Bruno L. Oliveira、João D. G. Correia、Isabel C. Santos、Isabel Santos、Bernhard Spingler、Roger Alberto

  DOI：10.1039/c002796k

  日期：——

  The labelling of targeting biomolecules requires small and hydrophilic complexes in order to not affect the binding properties of the vectors. 2,3-Diamino propionic acid (dap) is a small and strong, albeit scarcely used, tripod ligand for the fac-[99mTc(CO)3]+ moiety. We have introduced at the α-carbon atom in the basic dap structure various second functionalities such as carboxylato, amino and α-amino acid groups via various spacers in order to yield bifunctional chelators. These dap derivatives can be coupled to targeting molecules for application in molecular imaging. Full characterizations of the bifunctional chelators, X-ray structures of intermediates and of one rhenium complex, as well as labelling studies with 99mTc, are presented.

  靶向生物分子的标记需要小而亲水的复合物，以免影响载体的结合特性。2,3-二氨基丙酸（dap）是一种小巧且强力的三脚架配体，尽管使用较少，但适用于fac-[99mTc(CO)3]+基团。我们在基本的dap结构的α碳原子上引入了各种第二功能基团，如羧酸根、氨基和α-氨基酸基团，通过不同的连接体，以便获得双功能螯合剂。这些dap衍生物可以与靶向分子偶联，以应用于分子成像。本文展示了双功能螯合剂的完整表征，中间体和一个铼配合物的X射线结构，以及与99mTc的标记研究。
• Tricarbonyl M(I) (M = Re, 99mTc) complexes bearing acridine fluorophores: synthesis, characterization, DNA interaction studies and nuclear targeting
  作者：Teresa Esteves、Catarina Xavier、Sofia Gama、Filipa Mendes、Paula D. Raposinho、Fernanda Marques、António Paulo、João Costa Pessoa、José Rino、Giampietro Viola、Isabel Santos

  DOI：10.1039/c0ob00073f

  日期：——

  New pyrazolyl-diamine ligands with acridine derivatives at the 4-position of the pyrazolyl ring were synthesized and characterized (L1 and L2). Coordination towards the fac-[M(CO)3]+ (M = Re, 99mTc) led to complexes fac-[M(CO)3(κ3-L)] (L = L1: M = Re1, Tc1; L = L2: M = Re2, Tc2). The interaction of the novel pyrazolyl-diamine ligands (L1 and L2) and rhenium(I) complexes (Re1 and Re2) with calf thymus DNA (CT-DNA) was investigated by a variety of techniques, namely UV-visible, fluorescence spectroscopy and circular and linear dichroism. Compounds L1 and Re1 have moderate affinity to CT-DNA and bind to DNA by intercalation, while L2 and Re2 have a poor affinity for CT-DNA. Moreover, LD measurements showed that L1 and Re1 act as perfect intercalators. By confocal fluorescence microscopy we found that L1 and Re1 internalize and localize in the nucleus of B16F1 murine melanoma cells. The congener Tc1 complex also targets the cell nucleus exhibiting a time-dependent cellular uptake and a fast and high nuclear internalization (67.2% of activity after 30 min). Plasmid DNA studies have shown that Tc1 converts supercoiled (sc) puc19 DNA to the open circular (oc) form.

  合成并表征了新型噁唑基二胺配体，带有在噁唑环4位的氨基啶衍生物（L1和L2）。与fac-[M(CO)3]+（M = Re, 99mTc）的配位反应生成了配合物fac-[M(CO)3(κ3-L)]（L = L1: M = Re1, Tc1; L = L2: M = Re2, Tc2）。通过多种技术（即紫外可见光谱、荧光光谱以及圆二色性和线性二色性）研究了新型噁唑基二胺配体（L1和L2）及铼(I)配合物（Re1和Re2）与小牛胸腺DNA（CT-DNA）的相互作用。化合物L1和Re1对CT-DNA具有中等亲和力，并通过插层作用与DNA结合，而L2和Re2对CT-DNA的亲和力较差。此外，光谱测量显示L1和Re1作为完美的插层剂。通过共焦荧光显微镜，我们发现L1和Re1能够内部化并在B16F1小鼠黑色素瘤细胞的细胞核中定位。同类的Tc1配合物也靶向细胞核，表现出时间依赖性的细胞摄取以及快速而高效的核内部化（30分钟后活性达到67.2%）。质粒DNA研究表明，Tc1将超螺旋（sc）puc19 DNA转化为开放环状（oc）形式。