双（呋喃甲醛）缩二胺钴（II）配合物的合成及其氧合和催化氧化性能研究

合成和表征了氯化双（呋喃甲醛）缩邻苯二胺合钴（II）（1）、氯化双（呋 喃甲醛）缩乙二胺合钴（II）（2）、氯化双（呋喃甲醛）缩1，2-丙二胺合钴（ II）（3）和氯化双（呋喃甲醛）缩1，3-丙二胺合钴（II）（4）。在吡啶溶液中 和不同温度下，测定了配合物的饱和吸氧量，求出了氧加合常数和热力学参数ΔH °，ΔS°。并以这些配合物为催化剂，活化分子氧氧化环已烯得到高选择性的烯 丙位氧化产物。讨论了温度、配体结构对配合物氧合性能的影响和配体结构以及添 加NHPI（N-羟基邻苯二甲酰亚胺）对环已烯氧化反应的影响。

Synthesis, Oxygenation and Catalytic Performance of Cobalt(II) Complexes with N,N'-Bis(2-furaldehyde)diamine

N,N'-Bis(furaldehyde)-1,2-phenylenediamine cobalt(II) chloride (1), N,N'-bis(furaldehyde)-ethylenediamine cobalt(II) chloride (2), N,N'- bis(furaldehyde)-1,2-diaminopropane cobalt(II) chloride (3), N,N'-bis (furaldehyde)-1,3-diaminopropane cobalt(II) chloride (4) were prepared and characterized by IR, ~1H NMR and elemental analysis. The stoichiometries of dioxygen uptake by these complexes at different temperature in pyridine solution were determined. Their oxygenation equilibrium constants and thermodynamic data ΔH°, ΔS° were calculated. The catalytic activities and selectivities of the cobalt complexes in cyclohexene oxidation were examined. The influences of temperature and ligand structure on dioxygen affinity of the complexes were discussed. The order of catalytic activities of the cobalt complexes with different ligand is 1 > 4 > 3 > 2. The addition of N- hydroxyphthalimide (NHPI) significantly increases the rate of the catalytic oxidation and the selectivities for 2-cyclohexene-1-one formation.