{Re(CO)4(bpm)}CF3SO3 | 127335-55-1

• 英文名称: {Re(CO)4(bpm)}CF3SO3
• CAS: 127335-55-1
• 化学式: CF₃O₃S*C₁₂H₆N₄O₄Re
• 分子量: 605.481
• InChiKey: KUKJUPSGZHBXHX-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：

  吡啶 、 {Re(CO)4(bpm)}CF3SO3 以 吡啶 为溶剂， 以58.4%的产率得到[Re(2,2'-bipyrimidine)(CO)3(pyridine)](CF3SO3) * H2O
  参考文献：
  名称：

  Structure, Physical and Photophysical Properties, and Charge Separation Studies of Re(bpm)(CO)3Ln+ Complexes (L = CH3CN, py, MeQ+, py-PTZ)

  摘要：

  The synthesis, structure, and physical and/or photophysical properties of Re(bpm)(CO)(3)L(n+), where bpm is 2,2'-bipyrimidine and L = CH3CN, py (pyridine), MeQ(+) (N-methyl-4,4'-bipyridinium ion), and py-PTZ (10-(4-picolyl)phenothiazine), are described. The structure of [Re(bpm)(CO)(3)(CH3CN)]PF6 . 1/2CH(3)CN was determined by single-crystal X-ray diffraction. It crystallized in the space group P ($) over bar 1 with cell dimensions a = 10.089(11) Angstrom, b = 11.855(6) Angstrom, c = 18.990(6) Angstrom, alpha = 89.71(3)degrees, beta = 77.65(6)degrees, gamma = 65.83(6)degrees, Z = 4, and D-calcd = 2.082 g/cm(3). Of the 5565 reflections (Mo K alpha, 3.5 degrees less than or equal to 2 theta less than or equal to 45 degrees), 4721 reflections with F-0 > 3.0 sigma(F-0) were used in full-matrix least-squares refinement. Final residuals were R(F) = 0.0692 and R(w)(F) = 0.1026. The asymmetric unit contained two independent cations. The Re-N(bpm) bond distances were 2.171(9) and 2.198(10) Angstrom for one cation and 2.161(12) and 2.187(12) Angstrom for the other; the two Re-N(CH3CN) bond distances were 2.094(14) and 2.177(13) Angstrom, and the Re-C(CO) bond distances were 1.908(15), 1.938(17), and 1.912(12) Angstrom for the first cation and 1.897(15), 1.896(19), and 1.919(15) W for the second. The complexes exhibited three CO infrared-active bands in the 1900-2100 cm(-1) region and underwent optical transitions in the 300-350 nm region assigned to d pi(Re) --> pi*(bpm) transitions and in the 200-300 nm region assigned to intraligand pi --> pi* transitions. The complexes underwent multiple reductions attributed to reduction of coordinated bpm and MeQ(+). The first reduction of Re(bpm)(CO)(3)-py(+) was located at E(1/2) = -0.84 v VS SSCE, whereas the first reduction of Re(bpm)(CO)(3)MeQ(2+) was observed at E(1/2) = -0.70 V vs SSCE and was attributed to reduction of the MeQ(+) ligand. The only oxidations observed were for Re(bpm)(CO)(3)py-PTZ(+). These were located at E(1/2) values of 0.82 and 1.53 V vs SSCE and were attributed to oxidation of the py-PTZ ligand. Emission was observed from all the complexes in acetonitrile at room temperature except from Re(bpm)(CO)(3)py-PTZ(+). The emission quantum yields were low (Phi(em) = (0.5-2) x 10(-3)) and the emission lifetimes were short (tau similar to 2 ns). Transient absorption spectra revealed that charge separation occurred for both Re(bpm)(CO)(3)MeQ(2+) and Re(bpm)(CO)(3)py-PTZ(+) and involved transfer of an electron from Re(I) to MeQ(+) generating Re(II) and the MeQ(.) radical in the former and from py-PTZ to Re(II) forming the py-PTZ(+) radical cation and Re(I) in the latter. Intramolecular back electron transfer in [(bpm(-))Re-I(CO)(3)(py-PTZ(+))](+) occurred at a rate of 1.6 x 10(8) s(-1) and in [(bpm)Re-II(CO)(3)(MeQ(.))](2+) at a rate of 5.5 x 10(7) s(-1).

  DOI：

  10.1021/ic00126a013
• 作为产物：
  描述：

  五羰基氯铼(I) 、 silver trifluoromethanesulfonate 、 2 2'-联嘧啶 以 正己烷 、 二氯甲烷 为溶剂， 生成 {Re(CO)4(bpm)}CF3SO3
  参考文献：
  名称：

  高度发光的rh（I）杂环配体四羰基配合物

  摘要：

  描述了[Re（bpm）（CO）4 ]（BF 4）（bpm = 2,2'-bipyrimidine）的光物理性质和晶体结构：揭示了Re-C（CO）与CO的键距配体的反式彼此比对CO更长（2.03埃）配体的反式与BPM（1.93），并且所述阳离子发冷光强烈的乙腈（φ - [R 0.050，λ EM 543纳米，λ牛355纳米，τ390纳秒）在室温下进行还原淬灭，生成强力的有机和无机氧化剂。

  DOI：

  10.1039/c39900000179

文献信息

• Shaver, Randy J.; Rillema, D. Paul, Inorganic Chemistry, 1992, vol. 31, # 20, p. 4101 - 4107
  作者：Shaver, Randy J.、Rillema, D. Paul

  DOI：——

  日期：——