THEORETICAL STUDY OF SANDWICH COMPLEXES [Fe(η4 - E4)2]2- (E = N, P, As, Sb, AND Bi)
THEORETICAL STUDY OF SANDWICH COMPLEXES [Fe(η4 - E4)2]2- (E = N, P, As, Sb, AND Bi)
复制标题
DOI：
10.1142/s0219633607002988
复制
发表时间：
2007-06
影响因子：
2.4
通讯作者：
Zhiwei Li;Cunyuan Zhao;Liu-ping Chen
中科院分区：
文献类型：
--
作者：
Zhiwei Li;Cunyuan Zhao;Liu-ping Chen
用密度泛函理论（DFT）研究了Fe、E4 Fe和[Fe（η4 - E4）2]2-（E = N，P，As，Sb，Bi）物种的平衡几何构型、能量、谐振频率、稳定性和芳香性. E_4Fe和[Fe（η_4-E_4）_2]_2-体系的基态分别为Cs和D_4d结构。轨道分析表明，配体的π轨道与d 6铁中心的原子轨道之间的相互作用是[Fe（η4 - E4）2]2-（D4 d）配合物的主要成键模式. [Fe（η4 - E4）2]2-络合物的稳定性顺序为P > As > Sb > Bi > N。在与已知的二茂铁比较的基础上，NICS分析证实了[Fe（η_4-E_4）_2]_2-（D_4d）和二茂铁都是芳香族的。NICS分析表明，[Fe（η4 - E4）2]2-（D4 d）的芳香性主要是由于E-E π键和Fe孤对电子的作用。
The equilibrium geometries, energies, harmonic vibrational frequencies, stability, and aromaticities for the , E4Fe, and [Fe(η4 - E4)2]2- (E = N, P, As, Sb, and Bi) species are studied using density functional theory (DFT). The ground states of the E4Fe and [Fe(η4 - E4)2]2- systems are predicted to be Cs and D4d structures, respectively. Orbital analysis indicates that the orbital interactions between the π orbitals of the ligands and the atomic orbitals of the d6 iron center are the main bonding scheme for these [Fe(η4 - E4)2]2- (D4d) complexes. The stability of the [Fe(η4 - E4)2]2- complexes exhibits the order P > As > Sb > Bi > N for E. On the basis of comparison with the known ferrocene, the NICS analysis confirms that the [Fe(η4 - E4)2]2- (D4d) as well as ferrocene are aromatic. The dissected NICS reveals that the aromaticities of the [Fe(η4 - E4)2]2- (D4d) are primarily attributed to the effects of their E–E π bonds and Fe lone pairs.