l-bis(triphenylphosphine)iminium trans-dibromophthalocyaninato(2-)molybdate(III) | 196304-86-6

• 英文名称: l-bis(triphenylphosphine)iminium trans-dibromophthalocyaninato(2-)molybdate(III)
• CAS: 196304-86-6
• 化学式: C₃₂H₁₆Br₂MoN₈*C₃₆H₃₀NP₂
• 分子量: 1306.87
• InChiKey: GYYFHZVNWXKOIS-UHFFFAOYSA-L

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：
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反应信息

• 作为产物：
  描述：

  、 三苯基膦 以 not given 为溶剂， 生成 l-bis(triphenylphosphine)iminium trans-dibromophthalocyaninato(2-)molybdate(III)
  参考文献：
  名称：

  High Intensity Trip-Multiplet Transitions, a Reality! Synthesis, Properties, and Crystal Structure ofl-Bis(triphenylphosphine)iminiumtrans-Dibromophthalocyaninato(2-)molybdate(III)

  摘要：

  AbstractOxophthalocyaninato(2–)molybdenum(IV), activated by bromine oxidation prior to use, reacts with fused triphenylphosphine in the presence of bis(triphenylphosphine)iminium bromide to yield linear‐bis(triphenylphosphine)iminium trans‐dibromophthalocyaninato(2–)molybdate(III), l(PNP)trans[Mo(Br)2pc2−]. It crystallizes triclinic with crystal data: a = 10.506(1) Å, b = 12.436(2) Å, c = 12.918(2) Å, α = 76.186(1)°, β = 67.890(1)°, γ = 68.689(1)°; space group P1 (No. 2); Z = 1. MoIII is in a pseudo‐octahedral coordination geometry with the bromo ligands in trans‐arrangement. The MoNp and MoBr distance is 2.043(10) and 2.588(1) Å, respectively. The PNP cation adopts a linear conformation. In the IR spectrum vas(MoBr) is observed at 218 cm−1 and vas(PN) of the linear (PNP) core at 1406 cm−1. Cyclic and differential‐pulse voltammetry show two quasi‐reversible cathodic processes at −1.15 and −0.53 V vs. Ag/AgCl. The first is assigned to a phthalocyaninate directed reduction (pc2−/pc3−), while the latter arises from a Mo directed reduction (MoIII/MoII). Spectral monitoring confirms the reversible MoIII/MoII reduction. Two quasi‐reversible anodic processes at 0.60 and 1.27 V are assigned to the successive Mo directed oxidation with redox couples MoIII/MoIV and MoIV/MoV. For the first time, three very intense spin‐allowed trip‐quartet transitions are observed in the electronic absorption spectra at 7140 (TQI), 16890 (TQ2) and 18700 cm−1 (TQ3) together with a sing‐quartet transition at 15850 cm−1 and characteristic „Q”︁ region with maximum at 28500 cm−1 and „N”︁ region at 37400 cm−1. All electronic excitations are of comparable intensity. A prominent low temperature emission at 6690 cm−1 is assigned to a spin‐forbidden trip‐sextet.

  DOI：

  10.1002/zaac.19976230919