fac-[Re(methanol)₃(CO)₃](1+) | 160095-86-3

• 英文名称: fac-[Re(methanol)₃(CO)₃](1+)
• CAS: 160095-86-3
• 化学式: C₆H₁₂O₆Re
• 分子量: 366.365
• InChiKey: JEAVAFXRVAVYHQ-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：

  2-{[(4-甲基苯基)亚氨基]甲基}苯酚 、 fac-[Re(methanol)₃(CO)₃](1+) 以 甲醇 为溶剂， 反应 14.0h， 以174 mg的产率得到fac-[Re(2-(p-tolyliminomethyl)phenolato)(CO)₃(methanol)]
  参考文献：
  名称：

  Activation of Rhenium(I) Toward Substitution in fac-[Re(N,O′-Bid)(CO)₃(HOCH₃)] by Schiff-Base Bidentate Ligands (N,O′-Bid)

  摘要：

  A series of fac-[Re(N,O'-Bid)(CO)(3)(L)] (N,O'-Bid = monoanionic bidentate Schiff-base ligands with N,O donor atoms; L = neutral monodentate ligand) has been synthesized, and the methanol substitution reactions have been investigated. The complexes were characterized by NMR, IR, and UV-vis spectroscopy. X-ray crystal structures of the compounds fac-[Re(Sal-mTol)(CO)(3)(HOCH3)], fac-[Re(Sal-pTol)(CO)(3)(HOCH3)], fac-[Re(Sal-Ph)(CO)(3)(HOCH3)], and fac-[Re(Sal-Ph)(CO)(3)(Py)] (Sal-mTol = 2-(m-tolyliminomethyl)phenolato; Sal-pTol = 2-(p-tolyliminomethyl)phenolato; Sal-Ph = 2-(phenyliminomethyl)phenolato; Py = pyridine) are reported. Significant activation for the methanol substitution is induced by the use of the N,O bidentate ligand as manifested by the second order rate constants, with limiting kinetics being observed for the first time. Rate constants (25 degrees C) (k(1) or k(3)) and activation parameters (Delta Hk(double dagger), kJ mol(-1); Delta S-k(double dagger), J K-1 mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Re(Sal-mTol)(CO)(3)(HOCH3)] 3-chloropyridine: (k(1)) 2.33 +/- 0.01 M-1 s(-1); 85.1 +/- 0.6, 48 +/- 2; fac-[Re(Sal-mTol)(CO)(3)(HOCH3)] pyridine: (k(1)) 1.29 +/- 0.02 M-1 s(-1); 92 +/- 2, 66 +/- 7; fac-[Re(Sal-mTol)(CO)(3)(HOCH3)] 4-picoline: (k(1)) 1.27 +/- 0.05 M-1 s(-1); 88 +/- 2, 53 +/- 6; (k(3)) 3.9 +/- 0.03 s(-1); 78 +/- 8, 30 +/- 27; (k(f)) 1.7 +/- 0.02 M-1 s(-1); 86 +/- 2, 49 +/- 6; fac-[Re(Sal-mTol)(CO)(3)(HOCH3)] DMAP (k(3)) 1.15 +/- 0.02 s(-1); 88 +/- 2, 52 +/- 7. An interchange dissociative mechanism is proposed.

  DOI：

  10.1021/ic401115j
• 作为产物：
  描述：

  甲醇 、 (NEt4)2[rhenium(I)(bromide)3(carbonyl)3] 在 silver nitrate 作用下， 反应 26.0h， 生成 fac-[Re(methanol)₃(CO)₃](1+)
  参考文献：
  名称：

  Activation of Rhenium(I) Toward Substitution in fac-[Re(N,O′-Bid)(CO)₃(HOCH₃)] by Schiff-Base Bidentate Ligands (N,O′-Bid)

  摘要：

  A series of fac-[Re(N,O'-Bid)(CO)(3)(L)] (N,O'-Bid = monoanionic bidentate Schiff-base ligands with N,O donor atoms; L = neutral monodentate ligand) has been synthesized, and the methanol substitution reactions have been investigated. The complexes were characterized by NMR, IR, and UV-vis spectroscopy. X-ray crystal structures of the compounds fac-[Re(Sal-mTol)(CO)(3)(HOCH3)], fac-[Re(Sal-pTol)(CO)(3)(HOCH3)], fac-[Re(Sal-Ph)(CO)(3)(HOCH3)], and fac-[Re(Sal-Ph)(CO)(3)(Py)] (Sal-mTol = 2-(m-tolyliminomethyl)phenolato; Sal-pTol = 2-(p-tolyliminomethyl)phenolato; Sal-Ph = 2-(phenyliminomethyl)phenolato; Py = pyridine) are reported. Significant activation for the methanol substitution is induced by the use of the N,O bidentate ligand as manifested by the second order rate constants, with limiting kinetics being observed for the first time. Rate constants (25 degrees C) (k(1) or k(3)) and activation parameters (Delta Hk(double dagger), kJ mol(-1); Delta S-k(double dagger), J K-1 mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Re(Sal-mTol)(CO)(3)(HOCH3)] 3-chloropyridine: (k(1)) 2.33 +/- 0.01 M-1 s(-1); 85.1 +/- 0.6, 48 +/- 2; fac-[Re(Sal-mTol)(CO)(3)(HOCH3)] pyridine: (k(1)) 1.29 +/- 0.02 M-1 s(-1); 92 +/- 2, 66 +/- 7; fac-[Re(Sal-mTol)(CO)(3)(HOCH3)] 4-picoline: (k(1)) 1.27 +/- 0.05 M-1 s(-1); 88 +/- 2, 53 +/- 6; (k(3)) 3.9 +/- 0.03 s(-1); 78 +/- 8, 30 +/- 27; (k(f)) 1.7 +/- 0.02 M-1 s(-1); 86 +/- 2, 49 +/- 6; fac-[Re(Sal-mTol)(CO)(3)(HOCH3)] DMAP (k(3)) 1.15 +/- 0.02 s(-1); 88 +/- 2, 52 +/- 7. An interchange dissociative mechanism is proposed.

  DOI：

  10.1021/ic401115j

文献信息

• Effect of the triphenylphosphonium cation on the biological properties of new rhenium and technetium-99m fac-[M(CO)3(NSN)]±-type complexes: Synthesis, structural characterization, in vitro and in vivo studies
  作者：Achilleas Kyriazopoulos、Aikaterini-Lamprini Alexiou、Androulla Miliotou、Lefkothea Papadopoulou、Antonios Hatzidimitriou、Dionysia Papagiannopoulou

  DOI：10.1016/j.ica.2020.119807

  日期：2020.10

  Triphenylphosphonium (TPP) cations have been used for the development of tumor or myocardial diagnostic radiopharmaceuticals. In this work, the development of new [Tc-99m][Tc(CO)(3)(N,S,N)](+) complexes of the (N,S,N) tridentate chelator benzimidazol-2-yl-methylthioethylamine (L), and its triphenylphosphonium (TPP) cation derivative L-TPP is described. The TPP-moiety was conjugated at the N-tau-benzimidazol position of L. The reaction of the chelators L and L-TPP with a suitable precursor [Re(sol)(3)(CO)(3)](+) yielded single products of ReL+ and ReL-TPP2+. The complexes were characterized by spectroscopic methods and furthermore the structure of ReL was elucidated by X-ray crystallography. The respective Tc-99m-radiotracers were synthesized in high yield, their lipophilicity was measured and both exhibited high stability in cysteine, histidine solutions as well as in rat plasma. The in vitro cell studies in human erythroleukemia K-562 and glioblastoma U-87MG tumor cells showed that the tracer (TcL+)-Tc-99m exhibited significantly higher cellular uptake, while (TcL)-Tc-99m-TPP2+ exhibited sig-nificantly higher mitochondrial accumulation. The tracers (TcL+)-Tc-99m and 99mTcL-TPP2+ exhibited fast blood elimination and excretion via the hepatobiliary and the renal routes after intravenous administration in healthy mice. Tracer (TcL+)-Tc-99m exhibited higher myocardial uptake and renal excretion, while (TcL)-Tc-99m-TPP2+ exhibited primarily hepatobiliary excretion. These data confirm the high mitochondrial accumulation of (TcL)-Tc-99m-TPP2+ in vitro and show its potential as a candidate for tumor imaging.