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用密度泛函理论杂化密度泛函B3LYP方法研究了E24-,[CoE4]+和[P4CoE4]-(E=N,P,As,Sb,Bi)几何结构、键能及芳香性.结果表明,E42-,[CoE4]+和[P4CoE4]-的基态结构分别具有D4h,C4v和C4v(交错型)对称性.三明治配合物中,金属与配体间存在σ,π和δ三种成键方式,P4与E4间相互影响较小.E4对P4中的P—P键长影响随着N,P,As,Sb,Bi顺序逐渐变长,中心Co离子与E4间的键合能随N,P,As,Bi,Sb的顺序增大.N42-的环外具有弱芳香性,其它E42-环中心及环外均为反芳香性.除[CoN4]+外,其它[CoE4]+中的E4环均具有较强的中心和内芳香性及弱的外反芳香性.[P4CoE4]-中的P4和E4均具有较大的中心、内和外芳香性,且P4环芳香性随N,P,As,Sb,Bi顺序逐渐递增.
The geometrical structures, bond energies and aromaticities of E24 -, [CoE4] + and [P4CoE4] - (E = N, P, As, Sb, Bi) were investigated by density functional theory (B3LYP) , The ground state structures of E42 -, [CoE4] + and [P4CoE4] - have the symmetry of D4h, C4v and C4v (interlaced type) respectively.In the sandwich complex, there are three bonds of σ, π and δ P4, and E4, and the influence of P4 on the P-P bond length in P4 gradually becomes longer with the sequence of N, P, As, Sb and Bi, and the bond energy between the center Co ion and E4 increases with N , The order of P, As, Bi and Sb increases.N42- has a weak aromaticity outside the ring, and other E42-rings center and outside the ring are anti-aromatic.In addition to [CoN4] + other [CoE4] + Of the E4 rings have strong center and internal aromatic and weak external anti-aromatic [P4CoE4] - P4 and E4 have larger center, inside and outside the aromatic, and P4 aromatic ring with N , P, As, Sb, Bi gradually increase the order.