有机铂[PtCl(NCN-OH)]的密度泛函理论研究(英文)

A Density Function Theory Study of Organoplatinum [PtCl(NCN-OH)]

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。

Structural and electronic properties of para - hydroxyaryldiamineplatinum complex [PtCl （NCN - OH） ] and its dimer [ PtCl （NCN - OH） ]2 have been investigated using density function theory method B3LYP/LanL2D. The optimized ground state structure （Cs,^1A＇） of [PtCl（NCN- OH）] agrees well with x- ray diffraction data. Charge distribution analysis shows that the H atom in phenolic group O - H possesses the highest positive charge among all hydrogen atoms and it is this atom that plays the central role in the formation of the O - H - - - C1 - Pt intermolecular hydrogen bond in both α - and β - type network crystals. Calculated formation enthalpy △Hf°of the dimer relative to two separated complex units is about 47.3 kJ mol^-1, approximately doubling the hydrogen bond enthalpy of 22.7 kJ mol^-1 estimated from IR measurement. Replacement of Pt（Ⅱ） with Pd（Ⅱ） and Ni（Ⅱ） introduces slight structural changes and HOMO-LUMO gap variations, but causes significant charge redistribution around the metal centers.