fac-[Re(Acac)(CO)₃(Py)] | 58932-48-2

• 英文名称: fac-[Re(Acac)(CO)₃(Py)]
• 英文别名: fac-[Re(Acac)(CO)₃(pyridine)]；fac-Re(acac)(pyridine)(CO)3
• CAS: 58932-48-2；71117-20-9
• 化学式: C₁₃H₁₂NO₅Re
• 分子量: 448.449
• InChiKey: LUDHALKHJMLLTB-UHFFFAOYSA-N

计算性质

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

反应信息

• 作为产物：
  描述：

  吡啶 、 fac-[Re(Acac)(CO)₃(CH₃OH)] 以 甲醇 为溶剂， 反应 1.33h， 生成 fac-[Re(Acac)(CO)₃(Py)]
  参考文献：
  名称：

  Illustration of the electronic influence of coordinated β-diketone type ligands: A kinetic and structural study

  摘要：

  Beta-diketone type bidentate ligands (acetylacetone - AcacH, trifluoroacetylacetone - TfaaH and hexafluoroacetylacetone - HfaaH) were used in the synthesis of the neutral complexes,fac-Re(CO)(3)(Acac)(H2O)] (1), fac-[Re(CO)(3)(Tfaa)(H2O)] (2) and fac-[Re(CO)(3)(Hfaa)(H2O)] (3), using the (2 + 1) mixed ligand approach. The complexes were characterised by IR, NMR and X-ray crystallography. A new Re(I) crystal structure, fac-Re(CO)(3)(Hfaa)(Py)] (4) (with Py = pyridine) is reported, presenting a distorted octahedral coordination of the ligands around the metal centre. A kinetic study, involving the methanol substitution of fac-Re(CO)(3)(Acac)(CH3OH)] (5), fac-[Re(CO)(3)(Tfaa)(CH3OH)] (6) and fac-[Re(CO)(3)(Hfaa)(CH3OH)] (7), by pyridine as entering monodentate ligand, is investigated. The following second-order rate constants, were obtained for (5), (6) and (7) respectively at 25.0 degrees C; forward reaction rate constants: k(1) (M-1 s(-1)) = (13.7 +/- 0.1) x 10(-3), (0.35 +/- 0.03) x 10(-3) and (0.17 +/- 0.03) x 10(-3); reverse rate constants: k(-1) (s(-1))= (0.03 +/- 0.02) x 10(-3), (0.018 +/- 0.004) x 10(-3) and (0.013 +/- 0.004) x 10(-3) and stability constants: K-1 (M-1) = 457 +/- 305, 19 +/- 5 and 13 +/- 5. The activation parameters from the Eyring plots for the CH3OH substitution for (5) with Py are: Delta H-double dagger = 64 +/- kJ mol(-1) and Delta S-double dagger= -65 +/- 5 J K-1 mol(-1), indicative of an associative interchange type mechanism. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2014.08.005

文献信息

• Metal-Assisted In Situ Formation of a Tridentate Acetylacetone Ligand for Complexation of <i>fac</i>-Re(CO)₃⁺ for Radiopharmaceutical Applications
  作者：Paul D. Benny、Glenn A. Fugate、Adam O. Barden、Jennifer E. Morley、Elsa Silva-Lopez、Brendan Twamley

  DOI：10.1021/ic701996e

  日期：2008.4.1

  Reaction of [NEt4](2)[ReBr3(CO)(3)] with 2,4-pentanedione (acac) yields a complex of the type fac-Re(acac)(OH2)(CO)(3) (1) under aqueous conditions. 1 was further reacted with a monodentate ligand (pyridine) to yield a fac-Re(acac)(pyridine)(CO)(3) complex (2). Complex 1 was found to react with primary amines to generate a Schiff base (imine) in aqueous solutions. When a mixed-nitrogen donor bidentate ligand, 2-(2-aminoethyl)pyridine, that has different coordination affinities for fac-Re(acac)(OH2)(CO)(3) was utilized, a unique tridentate ligand was formed in situ utilizing a metal-assisted Schiff base formation to yield a complex fac-Re(CO)(3)(3[(2-phenylethyl)imino]-2-pentanone) (3). Tridentate ligand formation was found to occur only with the Re-coordinated acac ligand. Reactions of acac with fac-Re(CO)(3)Br(2-(2-aminoethyl)pyridine) (4) or a mixture of [NEt4](2)[ReBr3(CO)(3)], acac, and 2-(2-aminoethyl)pyridine did not yield the formation of complex 3 in water.