[Co(III)(2,4-di(tert-butyl)-6-(bis(2-pyridylmethyl)aminomethyl)phenolate)(3,5-di(tert-butyl)catecholate)]*CH3CN | 946578-83-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [Co(III)(2,4-di(tert-butyl)-6-(bis(2-pyridylmethyl)aminomethyl)phenolate)(3,5-di(tert-butyl)catecholate)]*CH3CN
• 英文别名: Acetonitrile;2-[[bis(pyridin-2-ylmethyl)amino]methyl]-4,6-ditert-butylphenolate;cobalt(3+);3,5-ditert-butylbenzene-1,2-diolate
• CAS: 946578-83-2
• 化学式: C₂H₃N*C₄₁H₅₄CoN₃O₃
• 分子量: 736.944
• InChiKey: HCIQFLDLWANOMF-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  8.3
• 重原子数：
  51
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  122
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [Co(III)(2,4-di(tert-butyl)-6-(bis(2-pyridylmethyl)aminomethyl)phenolate)(3,5-di(tert-butyl)catecholate)]*CH3CN 在 (NH₄)2Ce(NO₃)6 作用下， 以 乙腈 为溶剂， 生成 [Co(2,4-di(tert-butyl)-6-(bis(2-pyridylmethyl)aminomethyl)phenolate)(3,5-di(tert-butyl)semiquinonate)](2+)
  参考文献：
  名称：

  Formation and Characterization of Co(III)−Semiquinonate Phenoxyl Radical Species

  摘要：

  Co(III) complexes of N3O-donor tripodal ligands, 2,4-di(tert-butyl)-6-{[bis(2-pyridyl)methyl]aminomethyl}phenolate (tbuL), 2,4-di(tert-butyl)-6-{[bis(6-methyl-2-pyridyl)methyl]aminomethyl}phenolate (tbuL(Mepy)(2)), were prepared, and precursor Co(II) complexes, [Co(tbuL)Cl] (1) and [Co(tbuL(Mepy)(2))Cl] (2), and ternary Co(III) complexes, [Co(tbuL)(acac)]ClO4 (3), [Co(tbuL)(tbu-cat)] (4), and [Co(tbuL(Mepy)(2))(tbu-SQ)]ClO4 (5), where acac, tbu-cat, and tbu-SQ refer to pentane-2,4-dionate, 3,5-di(tert-butyl)catecholate, and 3,5-di(tert-butyl)semiquinonate, respectively, were structurally characterized by the X-ray diffraction method. Complexes 3 and 5 have a mononuclear structure with a fac-N3O3 donor set, while 4 has a mer-N3O3 structure. The cyclic voltammogram (CV) of complex 3 exhibited one reversible redox wave centered at 0.93 V (vs Ag/AgCl) in CH3CN. Complex 5 was converted to a phenoxyl radical species upon oxidation with Ce(IV), showing a characteristic pi-pi* transition band at 412 nm. The ESR spectrum at low temperature and the resonance Raman spectrum of 3 established that the radical species has a Co(III)-phenoxyl radical bond. On the other hand, the CVs showed two oxidation processes at E-1/2 = 0.01 and E-pa = 0.92 V for 4 and E-1/2a = 0.05 and E-1/2b = 0.69 V for 5. The rest potential of 4 (-0.11 V) was lower than the E-1/2 value, whereas that of 5 (0.18 V) was higher, indicating that the first redox wave of 4 and 5 is assigned to the tbu-cat and the tbu-SQ redox process, respectively. One-electron oxidized 4 showed absorption, resonance Raman, and ESR spectra which are similar to those of 5, suggesting formation of a stable Co(III)-semiquinonate species, which has the same oxidation level of 5. The resonance Raman spectrum of two-electron oxidized 4 showed the nu(8a) bands of the semiquinonate and phenoxyl radical, which were absent in the spectrum of one-electron oxidized 5. Since both oxidized species were ESR inactive at 5 K, the former was concluded to be a biradical species containing semiquinonate and phenoxyl radicals coupled antiferromagnetically and the latter to a species with a coordinated quinone.

  DOI：

  10.1021/ic700596g
• 作为产物：
  描述：

  3,5-二叔丁基邻苯二酚 、 [Co(2,4-di(tert-butyl)-6-(bis(2-pyridylmethyl)aminomethyl)phenolate)Cl]*CH3CN 在 N(C₂H₅)3 作用下， 以 乙腈 为溶剂， 生成 [Co(III)(2,4-di(tert-butyl)-6-(bis(2-pyridylmethyl)aminomethyl)phenolate)(3,5-di(tert-butyl)catecholate)]*CH3CN
  参考文献：
  名称：

  Formation and Characterization of Co(III)−Semiquinonate Phenoxyl Radical Species

  摘要：

  Co(III) complexes of N3O-donor tripodal ligands, 2,4-di(tert-butyl)-6-{[bis(2-pyridyl)methyl]aminomethyl}phenolate (tbuL), 2,4-di(tert-butyl)-6-{[bis(6-methyl-2-pyridyl)methyl]aminomethyl}phenolate (tbuL(Mepy)(2)), were prepared, and precursor Co(II) complexes, [Co(tbuL)Cl] (1) and [Co(tbuL(Mepy)(2))Cl] (2), and ternary Co(III) complexes, [Co(tbuL)(acac)]ClO4 (3), [Co(tbuL)(tbu-cat)] (4), and [Co(tbuL(Mepy)(2))(tbu-SQ)]ClO4 (5), where acac, tbu-cat, and tbu-SQ refer to pentane-2,4-dionate, 3,5-di(tert-butyl)catecholate, and 3,5-di(tert-butyl)semiquinonate, respectively, were structurally characterized by the X-ray diffraction method. Complexes 3 and 5 have a mononuclear structure with a fac-N3O3 donor set, while 4 has a mer-N3O3 structure. The cyclic voltammogram (CV) of complex 3 exhibited one reversible redox wave centered at 0.93 V (vs Ag/AgCl) in CH3CN. Complex 5 was converted to a phenoxyl radical species upon oxidation with Ce(IV), showing a characteristic pi-pi* transition band at 412 nm. The ESR spectrum at low temperature and the resonance Raman spectrum of 3 established that the radical species has a Co(III)-phenoxyl radical bond. On the other hand, the CVs showed two oxidation processes at E-1/2 = 0.01 and E-pa = 0.92 V for 4 and E-1/2a = 0.05 and E-1/2b = 0.69 V for 5. The rest potential of 4 (-0.11 V) was lower than the E-1/2 value, whereas that of 5 (0.18 V) was higher, indicating that the first redox wave of 4 and 5 is assigned to the tbu-cat and the tbu-SQ redox process, respectively. One-electron oxidized 4 showed absorption, resonance Raman, and ESR spectra which are similar to those of 5, suggesting formation of a stable Co(III)-semiquinonate species, which has the same oxidation level of 5. The resonance Raman spectrum of two-electron oxidized 4 showed the nu(8a) bands of the semiquinonate and phenoxyl radical, which were absent in the spectrum of one-electron oxidized 5. Since both oxidized species were ESR inactive at 5 K, the former was concluded to be a biradical species containing semiquinonate and phenoxyl radicals coupled antiferromagnetically and the latter to a species with a coordinated quinone.

  DOI：

  10.1021/ic700596g