manganese trisacetylacetonate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: manganese trisacetylacetonate
• 英文别名: In(acac)3；nickel(3+);(Z)-4-oxopent-2-en-2-olate
• 化学式: C₁₅H₂₁NiO₆
• 分子量: 356.018
• InChiKey: QEQMJOIECAPFJK-LNTINUHCSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -0.48
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  120
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为试剂：
  描述：

  4-溴苯腈 、 <2,5-(N,N,N',N'-tetramethyldiamino)phenyl>zinc chloride 在 manganese trisacetylacetonate 、 二异丁基氢化铝 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以21%的产率得到4-<2',5'-(N,N,N',N'-tetramethyldiamino)biphenyl>benzonitrile
  参考文献：
  名称：

  Charge transfer in covalently-linked porphyrin-donor complexes from picosecond transient absorption spectroscopy

  摘要：

  Octaalkyl free base porphyrins have been synthesized with covalently attached electron donors at a single meso position. Singlet-state lifetimes were determined from fluorescence quenching in three solvents and were found to be less-than-or-equal-to 1.5 ps for the N,N,N,N'-tetramethyl-1,4-phenylenediamine (TMPD) appended complex, 1.3 ns for the phenyl-TMPD-appended complex, and greater-than-or-equal-to 5 ns for the phertyl-appended, N,N-dimethylaniline (DMA) appended, and DMA-TMPD-appended porphyrin complexes in o-difluorobenzene. Single photon counting measurements and fluorescence quantum yield quenching studies of the phenyl-appended control and phenyl-TMPD charge-transfer complex gave 14 +/- 3 and 2 +/- 0.3 ns excited-state lifetimes, respectively. Fluorescence quantum yields of the TMPD and phenyl-TMPD porphyrins were higher in solvents with lower dielectric constants. Picosecond absorption spectroscopy was performed on molecules exhibiting fluorescence quenching to characterize the charge-transfer state and to determine the recombination kinetics. Conclusive evidence of charge transfer was obtained by observing the donor cation absorption at 606 nm for the TMPD and phenyl-TMPD porphyrins. Picosecond absorption changes in the 380-500-nm region are complete within 50 ps for the TMPD-appended free base porphyrin and 11.5 ns for the phenyl-TMPD-appended free base porphyrin. First-order kinetic analysis indicates that the charge recombination rates are 26 +/- 3 ps and 3.5 +/- 0.4 ns for the TMPD-appended and phenyl-TMPD-appended complexes, respectively. These data yield beta = 0.8-1.1 angstrom-1 for the exponent in the distance dependence of the electron-transfer rate, exp{-beta(r-r0)}. Inasmuch as similar beta values have been determined for electron transfer through saturated bonds, it can be concluded that the pi system of the meso substituents is ineffective in mediating electron transfer, as expected from the near orthogonality of the porphyrin and substituent rings. This is the first systematic study of electron transfer in porphyrin-donor complexes.

  DOI：

  10.1021/j100137a021