| 136019-18-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• CAS: 136019-18-6
• 化学式: C₃₈H₅₀Co₂N₁₄O₆S₄
• 分子量: 1045.16
• InChiKey: FXMFTAACOFWPDM-UHFFFAOYSA-J

反应信息

• 作为产物：
  描述：

  在 O₂ 作用下， 以 硝基苯 为溶剂， 生成
  参考文献：
  名称：

  Stoichiometry, products and kinetics of oxidation of neutral 2,6-diacetylpyridine-bis(N4-azacyclic thiosemicarbazone)cobalt(II) complexes by dioxygen in aprotic solvents

  摘要：

  Low-spin, square planar cobalt(II) complexes are obtained by reaction of equimolar cobalt(II) acetate with potentially five-coordinate 2,6-diacetylpyridine-bis(N4-azacyclic thiosemicarbazone) ligands. When the N4-azacyclic moiety is piperidyl, morpholyl and N-methylpiperazyl, the cobalt(II) complexes are abbreviated as [Co(DAPP)], [Co(DAPM)] and [Co(DAPN)], respectively. The complexes are freely soluble in methylene chloride and nitrobenzene. They rapidly react with dioxygen in these solvents to form the corresponding diamagnetic mu-peroxodicobalt(III) complexes with stoichiometry 2Co(II) + O2 --> (Co(III))2O2, as indicated by manometric oxygen uptake, cryoscopic measurements in nitrobenzene and the appearance of a v(O-O) band at 860 cm-1. Comparison of the infrared spectra of the cobalt(II) and cobalt(III) complexes and the H-1 NMR spectra of cobalt(III) complexes with corresponding data for the structurally known nickel(II) complex [Ni(DAPM)] indicates that the bis-thiosemicarbazone ligands act as dibasic tetradentate molecules. However, cobalt is unsymmetrically bonded to the thiohydrazone portions of the ligand. Reduction of dioxygen to bound peroxide by large excesses of these cobalt(II) complexes in nitrobenzene and methylene chloride is governed by the third-order rate law d[(Co(III))2O2]/dt = k2[co(II)]2[O2]. Very negative DELTA-S2#, small DELTA-H2# and minimal solvent effects suggest that assembly of the activated complex is rate-determining. Rate constants k2 at 25-degrees-C decrease in order [Co(DAPN)] > [Co(DAPM] > [Co(DAPP)].

  DOI：

  10.1016/s0020-1693(00)83070-4