【摘要】 在B3LYP/6-31G(d, p)水平上,用全电子分别研究了Mg2+、Ca2+、Mn2+、Co2+、Ni2+、Cu2+和Zn2+与磷酸二甲酯(DMP-)“双齿”配位模式下的相互作用,且由4个水分子((H2O)4)“饱和”各金属离子六配位模式下的其它位点。结果表明:这种配位模式下,DMP-对上述金属离子的选择性顺序为:Cu2+>Ni2+>Zn2+>Co2+>Mg2+>Mn2+>Ca2+,和Irving-Williams序列基本一致。且具有未充满d层轨道的金属对配体的变化“响应”明显。通过NBO(自然键轨道)方法对配合物电荷布居分析可得出主族金属离子与配体间以静电相互作用为主,非主族金属离子配合物中存在一定的共价作用的结论,同时关于配合物各部分间键轨道相互作用的分析部分的反映了金属离子与配体的作用实质。更多还原

【Abstract】 The interactions of dimethyl phosphate anion (DMP-) with Mg2+, Ca2+, Mn2+, Co2+, Ni2+, Cu2+ and Zn2+ cations were calculated with DFT/B3LYP method by using the standard 6-31G(d,p) basis set, while the remaining coordination bonds are saturated with water molecules ((H2O)4). All geometries were optimized without symmetry restrictions. The interaction energies of complexes provide a comparatively reliable quantification of the selectivity of dimethyl phosphate anion for the studied metal ions, which is in reasonable agreement with the Irving-Williams list. Moreover, the cations with an unfilled state of d-electrons may be sensitive to the changing of ligands. In addition, the population of changes of the complexes and the significant donor-acceptor natural bond orbital interaction were analyzed with the method of Natural Bond Orbital analysis.更多还原