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本文采用密度泛函方法B3LYP/LanL2D研究了有机铂配合物[PtCl(NCN -OH) ]及其双体的几何结构和电子性质。[PtCl(NCN -OH) ]的基态结构与X -射线衍射结构良好吻合。集居数分析表明,酚羟基氢在所有氢原子中具有最高正电荷,是形成O -H - - -Cl-Pt分子间氢键的关键。计算双体形成焓ΔHf°=4 7.3km·mol- 1约是其氢键键能红外估计值的两倍。用Ni或Pd替代Pt,配合物结构和HOMO -LUMO能隙宽度发生微小变化,但导致金属中心周围电荷分布的显著不同。
In this paper, the geometrical and electronic properties of organic platinum complexes [PtCl (NCN-OH)] and their cations were studied by density functional method B3LYP / LanL2D. The ground state structure of [PtCl (NCN-OH)] is in good agreement with that of X - ray diffraction. The population analysis shows that the phenolic hydroxyl hydrogen has the highest positive charge among all the hydrogen atoms and is the key to form the hydrogen bond between the O -H - and -Cl-Pt molecules. Calculating the enthalpy of formation of the enthalpy ΔHf ° = 4 7.3 km · mol -1 is about twice as high as the infrared estimate of the hydrogen bond energy. Substituting Pt for Ni or Pd, there is a slight change in the width of the energy gap of the complex structure and the HOMO-LUMO, but results in a significant difference in charge distribution around the metal center.