运用高精度密度泛函B3LYP/6-311+G*方法,对(BCO)5M和[(BCO)5]2M(M=L i+,Na+,K+,Be2+,Mg2+,Ca2+)16种配合物的经典几何构型(正五角单锥(C5v),交错式(D5d)和重叠式(D5h))进行了理论计算.优化构型稳定,对称性高.同系配合物中,RB-C值在同一主族中从上到下依次减小,而同一周期中则从左到右依次增大,RB-M值的变化规律与之相反.所有配合物中,B均带负电荷,且都比基本配体1([(BCO)5]-)中的多.金属M所带正电荷(同一系列配合物中)随着主量子数的增大而增大,C则相反;同时随着质量数的增大,C和M所带正电荷均呈增大趋势.这些变化均与金属离子所带电荷和原子半径有关.分子轨道的分析阐述了配合物的成键本质.同时还从HOMO轨道能量预测出这些配合物的第一电离势,具有实际参考意义. (BCO) 5M and 16 complexes of [(BCO) 5] 2M (M = L i +, Na +, K +, Be2 +, Mg2 +, Ca2 +) were synthesized by using B3LYP / 6-311 + G * The classical geometrical configurations (C5v, D5d and D5h) are theoretically calculated with the optimized configuration and high symmetry.The RB-C values ​​of the homologous complexes are the same In the main group, the order decreases from top to bottom, and the order increases from left to right in the same period, while the variation law of RB-M value is opposite. In all the complexes, B is negatively charged, Ligand 1 ([(BCO) 5] -), the positive charge of metal M (in the same series of complexes) increases with the increase of the main quantum number, while C is the opposite. , And the positive charges of C and M all increase.These changes are related to the charge and atomic radius of the metal ions.The analysis of the molecular orbitals expounds the bonding nature of the complexes.At the same time, Prediction of the first ionization potential of these complexes has practical significance.