| 226956-33-8

• CAS: 226956-33-8
• 化学式: C₅₃H₃₇ClCoN₅
• 分子量: 838.356
• InChiKey: HCPNCJLQKXQQBN-NBICUONBSA-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：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  [5,10,15,20-tetraphenylporphyrin]cobalt(III) chloride 、 2, 6-二甲基苄氰 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Laser Photolysis Studies on Photodissociation of Axial Ligands from Isocyanide Complexes of Cobalt(III) and Rhodium(III) Porphyrins in Toluene Solutions. A Comparison with the Photochemistry of Carbonylrhodium(III) Porphyrin

  摘要：

  Chlorocobalt(III) and iodorhodium(III) tetraphenylporphyrins, (CI)(CoTPP)-T-III and (I)(RhTPP)-T-III, react with 2,6-dimethylphenyl isocyanide (R-NC) in toluene solutions to give the isocyanide complexes, (Cl)(R-NC)(CoTPP)-T-III and (I)(R-NC)(RhTPP)-T-III, respectively. The 355-nm laser photolysis studies have shown that these complexes photodissociate the axial ligand, R-NC. The quantum yield phi, for the photodissociation of R-NC from (CI)(R-NC)(CoTPP)-T-III is determined as 0.091 in both degassed and oxygen-saturated toluene. On the other hand, (I)(R-NC)(RhTPP)-T-III gives phi = 0.19 in degassed toluene and phi = 0.07 in oxygen-saturated toluene. The dissociation of R-NC from (I)(R-NC)(RhTPP)-T-III was confirmed to occur from both the excited singlet and tripler states by transient spectroscopic measurements. The small quantum yield obtained with the oxygen-saturated solution is explained by the quenching of the triplet state, (3)(pi,pi*) of (I)(R-NC)(RhTPP)-T-III. The triplet state decays with a rate constant 9.5 x 10(4) s(-1) in degassed toluene and is effectively quenched by oxygen with a bimolecular rate constant 6.7 x 10(8) M-1 s(-1). In comparison with (I)(R-NC)(RhTPP)-T-III, the lifetime of the (3)(pi,pi*) State of (CI)(R-NC)(CoTPP)-T-III is too short to be detected by the present laser photolysis system, probably because of the very fast radiationless process, (3)(pi,pi*) --> (3)(pi,d(z)(2)) --> (3)(d pi,d(z)(2)). The dissociation of R-NC from (Cl)(R-NC)(CoTPP)-T-III is assumed to occur from the (3)(d pi,d(z)(2)) state. The long lifetime of the (3)(pi,pi*) State of (I)(R-NC)(RhTPP)-T-III is interpreted on the assumption that the (3)(d pi,d(z)(2)) is located higher in energy than the (3)(pi,pi*) state. The dissociation of R-NC from (I)(R-NC)(RhTPP)-T-III at the tripler slate is suggested to occur from the thermally populated (3)(d pi,d(z)(2)) state. The laser photolysis studies of carbonyl-rhodium(III) tetraphenylporphyrin are also described to elucidate the ligand dissociation mechanism of rhodium(III) porphyrins.

  DOI：

  10.1021/jp984287m