trans(P),cis(C)-[Re((C4H3N)2CC6H4CO2CH3)(CO)2(PPh3)(P(n-Bu)3)] | 1351797-60-8

• 英文名称: trans(P),cis(C)-[Re((C4H3N)2CC6H4CO2CH3)(CO)2(PPh3)(P(n-Bu)3)]
• CAS: 1351797-60-8
• 化学式: C₄₉H₅₅N₂O₄P₂Re
• 分子量: 984.141
• InChiKey: XUZUQSNOZKZCLQ-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：
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反应信息

• 作为产物：
  描述：

  三丁基膦 、 氘代乙腈 、 fac-[Re((C4H3N)2CC6H4CO2CH3)(CO)3(PPh3)] 以 氘代乙腈 为溶剂， 生成 trans(P),cis(C)-[Re((C4H3N)2CC6H4CO2CH3)(CO)2(PPh3)(P(n-Bu)3)]
  参考文献：
  名称：

  Luminescent Rhenium(I)-Dipyrrinato Complexes

  摘要：

  The first Re(I)-dipyrrinato complexes are reported. Complexes with the general formulas fac-[ReL(CO)(3)Cl](-), fac-[ReL(CO)(3)PR3], and [ReL(CO)(2)(PR3)(PR'(3))] have been prepared, where L is one of a series of meso-aryl dipyrrinato ligands. Access to these complexes proceeds via the reaction of [Re(CO)(5)Cl] with the dipyrrin (LH) to produce fac-[ReL(CO)(3)Cl](-). A subsequent reaction with PR3 (R = phenyl, butyl) leads to displacement of the chloride ligand to generate fac-[ReL(CO)(3)PR3], and further reaction with PR'(3) leads to the displacement of the CO ligand trans to the first PR3 ligand to give trans(P), cis(C)-[ReL(CO)(2)(PR3)(PR'(3))]. The structures of the complexes were determined in the solid state by X-ray crystallography and in solution by H-1 NMR spectroscopy. Electronic absorption spectroscopy reveals a prominent band in the visible region at relatively low energy (472-491 nm) for all complexes, which is assigned as a pi-pi* transition of the dipyrrin chromophore. Weak emission (lambda(ex) = 485 nm, quantum yields <0.01) was observed for [ReL(CO)(3)Cl](-) and [ReL(CO)(3)PR3] complexes, but no emission was generally evident from the [ReL(CO)(2)(PR3)(PR'(3))] complexes. On the basis of the large Stokes shift (similar to 6000 cm(-1)), the emission is ascribed to phosphorescence from a triplet excited state. The emission intensity is sensitive to dissolved oxygen and methyl viologen; a Stern-Volmer plot in the latter case gave a straight line. Photochemical ligand substitution reactions of [ReL(CO)(3)PR3] were induced by excitation with a 355 nm laser in acetonitrile. [ReL(CO)(2)(PR3)(CH3CN)] is formed as a putative intermediate, which reacts thermally with added PR'(3) to produce [ReL(CO)(2)(PR3)(PR'(3))] complexes.

  DOI：

  10.1021/ic201877t