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用密度泛函理论(DFT)研究了标题化合物的电子结构、电离能和稳定性。研究发现,体系的交错型(D4d)结构是稳定的,而重叠型(D4h)异构体则是过渡态。从垂直电离能的计算可知,Fe、Ru和Os的配合物对分子内的库仑排斥力而言是不稳定的,而Co、Rh和Ir的类似物则是稳定的。此外,计算结果表明,钠能作为抗衡离子来抵消分子内的库仑排斥力,使电子不会自发地离去,因为这样可以产生更稳定的结构,即[P4MP4Na]-,从而可以便于实验操作。另外,金属-配体裂解反应能的计算表明这些夹心型配合物都是热稳定的。
The electronic structure, ionization energy and stability of the title compound were studied by density functional theory (DFT). The study found that the staggered (D4d) structure of the system is stable, while the overlapping (D4h) isomers are transitional. From the calculation of the vertical ionization energy, the complexes of Fe, Ru and Os are unstable to intramolecular Coulomb repulsion while the analogues of Co, Rh and Ir are stable. In addition, the calculated results show that sodium acts as a counterion to counteract the intramolecular Coulomb repulsion, so that the electrons do not leave spontaneously, as this results in a more stable structure, namely [P4MP4Na] -, which facilitates the experimental operation. In addition, calculations of the metal-ligand cleavage reaction energies indicate that these sandwich-type complexes are all thermostable.