摘要
运用密度泛函理论(DFT),研究1,3,5-C3P3H3、(1,3,5-C3P3H3)M和(1,3,5-C3P3H3)2M(M=Li+-K+,Be2+-Ca2+)的结构、键和能以及芳香性.结果表明,1,3,5-C3P3H3、(1,3,5-C3P3H3)M和(1,3,5-C3P3H3)2M的基态结构分别为D3h、C3V和D3d对称性;(1,3,5-C3P3H3)2M的交错(D3d)和重叠(D3h)两种构型的旋转势能面较平坦,金属离子与配体间主要以静电作用相结合,第一、第二主族三明治配合物的解离方式不同,其中(1,3,5-C3P3H3)2Mg2+的解离能最大,配合物最稳定;除(1,3,5-C3P3H3)Mg2+和(1,3,5-C3P3H3)2Be2+为中心反芳香性外,其他配合物都具有芳香性,其中心芳香性较自由配体降低,且内侧芳香性大于外侧芳香性;芳香性的主要贡献来源是C-Pπ键,同主族三明治配合物的芳香性随着金属原子序数的增加而增强.
The equilibrium geometries,binding energies,and aromaticities of 1,3,5-C3P3H3,（1,3,5-C3P3H3）M and（1,3,5-C3P3H3）2M（M=Li^＋-K＋,Be^2＋-Ca^2＋） were calculated by the density function theory.The results indicate that the ground states of 1,3,5-C3P3H3,（1,3,5-C3P3H3）M and（1,3,5-C3P3H3）2M were in D3h,C3V and D3d symmetries,respectively.The potential energy surface of rotation between the staggered（D3d） and eclipsed（D3h） structure for（1,3,5-C3P3H3）2M is smooth.The main interactions between ligands and metal are electrostatic interactions.There are different dissociation ways for ⅠA and ⅡA complexes.（1,3,5-C3P3H3）2Mg2＋ has the largest dissociate energy,and is the stablest.Except for（1,3,5-C3P3H3）Mg2＋ and（1,3,5-C3P3H3）2Be2＋ having central anti-aromaticities,all of the other complexes have the lower central-aromaticities comparing to the ligand,and the stonger inner-aromaticities comparing to the outer-aromaticities.The contributions are dominated the C-P π bond.The aromaticity for the same group complexes increases with the order from Li to K,and form Be to Ca.
出处
《内蒙古师范大学学报（自然科学汉文版）》
CAS
2010年第5期510-519,共10页
Journal of Inner Mongolia Normal University(Natural Science Edition)
基金
内蒙古自然科学基金资助项目(20080404MS0203)
内蒙古师范大学研究生科研创新基金项目(CXJJS09043)
关键词
三磷苯
三明治配合物
结构
芳香性
密度泛函
triphosphabenzene
sandwich complex
structure
aromaticity
density functional theory
