fac-[Re(tropolonate)(CO)₃(H₂O)] | 1403758-47-3

• 英文名称: fac-[Re(tropolonate)(CO)₃(H₂O)]
• 英文别名: fac-[Re(tropolonato)(CO)₃(H₂O)]；fac-[Re(Trop)(CO)₃(H₂O)]
• CAS: 1403758-47-3
• 化学式: C₁₀H₇O₆Re
• 分子量: 409.369
• InChiKey: VLFXOCRDKUVRFJ-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：

  4-二甲氨基吡啶 、 fac-[Re(tropolonate)(CO)₃(H₂O)] 以 甲醇 为溶剂， 反应 1.0h， 以93%的产率得到fac-[Re(tropolonate)(CO)₃(4-dimethylaminopyridine)]
  参考文献：
  名称：

  不同单齿亲核试剂 在fac- [Re（Trop）（CO）3（MeOH）]中甲醇取代的环境和高压动力学研究†

  摘要：

  在甲醇替代FAC - [的Re（CO）3（特罗普）（MeOH）中]络合物（特罗普- = tropolonate）用范围的7点的亲核试剂，即吡啶（PY），4-二甲氨基吡啶（DMAP），咪唑（研究IM），硫脲（TU），1-甲基-2-硫脲（METU），溴（溴- ）和碘化（I - ）以可变的温度，并在环境和高压。通过NMR，IR和UV / vis光谱以及化学分析对取代产物进行表征，并通过fac- [Re（Trop）（CO）3（Im）]和fac- [Re （拖曳）（CO）3（DMAP）]。在fac- [Re（Trop）（CO）3（MeOH）]上于25°C在甲醇中对其中四个进入的亲核试剂进行高压动力学研究，得出以下活化体积ΔV ≠ （kL），用于通过由k L（cm 3 mol -1）定义的四个亲核试剂：Im：9.0±0.2；Py：10.1±0.2；TU：10.0±0.3，MeTU：14.5±0.3。由于这些实验ΔV

  DOI：

  10.1039/c9dt01528k
• 作为产物：
  描述：

  [Re₂(CO)₆(μ²-OH)₃]^- 以 水 为溶剂， 生成 fac-[Re(tropolonate)(CO)₃(H₂O)]
  参考文献：
  名称：

  Coordinated Aqua vs Methanol Substitution Kinetics in fac-Re(I) Tricarbonyl Tropolonato Complexes

  摘要：

  Water-soluble fac-[Re(CO)(3)(L,L'-Bid)(X)] (L,L'-Bid = tropolonato, X = H2O, methanol) complexes have been synthesized, and the aqua and methanol substitution reactions were investigated in water (pH range 6.3-10.0) and methanol, respectively, and compared. Thiocyanate ions were used as monodentate entering ligand. The complexes were characterized by UV-vis, IR. and NMR spectroscopy. The crystal structures of the complexes [NEt4] fac-[Re(Trop)(CO)(3)(H2O)]center dot NO3 center dot H2O (reactant) andfac-[Re(CO)(3)(Trop)(Py)], a substitution product, are reported. Overall it was found that the aqua substitution of fac-[Re(CO)(3)(Trop)(H2O)] is about 10 times faster than the methanol substitution reaction for fac-[Re(CO)(3)(Trop)(MeOH)], with forward and reverse rate and stability constants [k(1) (M-1 s(-1)), k(-1) (s(-1)), K-1, (M-1)] for thiocyanate as monodentate entering ligand as follows: fac-[Re(CO)(3)(Trop)(H2O)] = 2.54 +/- 0.03, 0.0077 +/- 0.0005, 330 +/- 22/207 +/- 14 and fac[Re(CO)(3)(Trop)(MeOH)] = 0.268 +/- 0.002, 0.0044 +/- 0.0002, (61 +/- 3)/(52 +/- 4). The activation parameters [Delta H-k1(double dagger)(kJ mol(-1))] Delta S-k1(double dagger) (J K(-1)f mol(-1))or the aqua and methanol complex respectively are 56.1 +/- 0.7, -49 +/- 2 and 64 +/- 1, -43 +/- 5.

  DOI：

  10.1021/ic301891u

文献信息

• Synthesis, characterization and substitution reactions of fac-[Re(O,O′-bid)(CO)3(P)] complexes, using the “2+1” mixed ligand model
  作者：Amanda-Lee Manicum、Orbett Alexander、Marietjie Schutte-Smith、Hendrik G. Visser

  DOI：10.1016/j.molstruc.2020.127953

  日期：2020.6

  were synthesised in high yield and purity, using the “2 + 1” mixed ligand concept and the characterisation was done by spectroscopic methods IR, NMR, UV/Vis and elemental analysis. A kinetic study of the methanol substitution of fac-[Re(CO)3(Acac)(CH3OH)] (2), fac-[Re(CO)3(Benzac)(CH3OH)] (6) fac-[Re(CO)3(Tfaa)(CH3OH)] (9) and fac-[Re(CO)3(Hfaa)(CH3OH)] (12), by triphenylphosphine - PPh3, cyclohexyl diphenylphosphine

  摘要 六种配合物的固态结构 fac-[Re(Acac)(CO)3(PPhCy2)] (3), fac-[Re(Acac)(CO)3(PCy3)] (4), fac-[ Re(Benzac)(CO)3(PPh3)] (7), fac-[Re(Tfaa)(CO)3(PPh3)] (10), fac-[Re(Hfaa)(CO)3(PPh3)] (13) 和 fac-[Re(Trop)(CO)3(PTA)] (15)}；据报道，乙酰丙酮 = Acac、三氟乙酰丙酮 = Tfaa、苯甲酰丙酮 = Benzac、六氟乙酰丙酮 = Hfaa 和 tropolone = Trop。使用“2 + 1”混合配体概念以高产率和纯度合成配合物，并通过光谱方法 IR、NMR、UV/Vis 和元素分析进行​​表征。fac-[Re(CO)3(Acac)(CH3OH)] (2), fac-[Re(CO)3(Benzac)(CH3OH)]
• Synthesis, characterization, kinetic investigation and biological evaluation of Re(<scp>i</scp>) di- and tricarbonyl complexes with tertiary phosphine ligands
  作者：Verity Lindy Gantsho、Mazzarine Dotou、Marta Jakubaszek、Bruno Goud、Gilles Gasser、Hendrik Gideon Visser、Marietjie Schutte-Smith

  DOI：10.1039/c9dt04025k

  日期：——

  Rhenium(i) di- and tri-carbonyl complexes of the form fac-[Re(CO)3(L,L'-Bid)X] and [Re(CO)2(L,L'-Bid)X2], where X = aqua (H2O), methanol (CH3OH), triphenylphosphine (PPh3), 1,3,5-triaza-7-phosphaadamantane (PTA), tricyclohexylphosphine (PCy3) and L,L'-Bid = O,O' bidentate ligands (tropolone = TropH and 3-hydroxyflavone = FlavH) and N,O bidentate ligands (8-hydroxyquinoline = QuinH, 5,7-chloro-8-hydroxyquinoline

  f（i）二和三羰基配合物，形式为fac- [Re（CO）3（L，L'-Bid）X]和[Re（CO）2（L，L'-Bid）X2]，其中X =水（H2O），甲醇（CH3OH），三苯膦（PPh3），1,3,5-三氮杂-7-磷金刚烷（PTA），三环己基膦（PCy3）和L，L'-投标= O，O'双齿配体（托洛酮= TropH和3-羟基黄酮= FlavH）和N，O二齿配体（8-羟基喹啉= QuinH，5,7-氯-8-羟基喹啉= diCl-QuinH和喹啉-2,4-二羧酸= QuinH2）合成了，并通过1H-，13C-和31P-NMR，IR，UV / Vis和显微分析进行了明确表征。fac- [Re（CO）3（QuinH）（ ）]· （5），fac- [Re（CO）3（Quin）（PPh3）]（11），fac-获得[Re（CO）3（diCl-Quin）（PPh 3）]（12）和[Re（CO）2（Trop）（PPh
• Crystal and molecular structures of<i>fac</i>-[Re(Bid)(PPh₃)(CO)₃] [Bid is tropolone (TropH) and tribromotropolone (TropBr₃H)]
  作者：Marietjie Schutte-Smith、Hendrik Gideon Visser

  DOI：10.1107/s205322962200465x

  日期：2022.6.1

  Two rhenium complexes, namely,fac-tricarbonyl(triphenylphosphane-κP)(tropolonato-κ²O,O′)rhenium(I), [Re(C₇H₅O₂)(C₁₈H₁₅P)(CO)₃] orfac-[Re(Trop)(PPh₃)(CO)₃] (1), andfac-tricarbonyl(3,5,7-tribromotropolonato-κ²O,O′)(triphenylphosphane-κP)rhenium(I), [Re(C₇H₂Br₃O₂)(C₁₈H₁₅P)(CO)₃] orfac-[Re(TropBr₃)(PPh₃)(CO)₃] (2) (TropH is tropolone and and TropBr₃H is tribromotropolone), were synthesized and their crystal and molecular structures confirmed by single-crystal X-ray diffraction. Both crystallized in the space groupP-1 and display an array of inter- and intramolecular interactions which were confirmed by solid-state¹³C NMR spectroscopy using cross polarization magic angle spinning (CPMAS) techniques, as well as Hirshfeld surface analysis. The slightly longer Re—P distance of1[2.4987 (5)versus2.4799 (11) Å for1and2, respectively] suggests stronger back donation from the carbonyl groups in the former case, possibly due to the stronger electron-donating ability of the unsubstituted tropolonate ring system. However, this is not supported in the Re—CO bond distances of1and2.

  两种铼配合物，即面-三羰基(三苯基膦-κP)(tropolonato-κO,O′)铼(I)、[Re(C7H5O2)(C18H15P)(CO)3]或fac-[Re(Trop)(PPh3)(CO)3](1)，以及fac-三羰基(3,5,7-三溴-κO,O′)(三苯基膦-κP)铼(I)、合成了[Re(C7H2Br3O2)( )(CO)3]或fac-[Re(TropBr3)(PPh3)(CO)3](2)（TropH 为三溴三苯酮，TropBr3H 为三溴三苯酮），并通过单晶 X 射线衍射证实了它们的晶体和分子结构。这两种化合物都在空间群 P-1 中结晶，并显示出一系列分子间和分子内相互作用，这些相互作用通过使用交叉偏振魔角旋光（CPMAS）技术的固态 13C NMR 光谱以及 Hirshfeld 表面分析得到了证实。1 和 2 的 Re-P 距离[分别为 2.4987 (5) Å 和 2.4799 (11) Å]稍长，这表明前者的羰基反向捐赠能力更强，这可能是由于未取代的三苯酚环系统具有更强的电子捐赠能力。然而，1 和 2 的 Re-CO 键距离并不支持这一观点。