title: Substitution effect on the geometry and electronic structure of the ferrocene.
abstract: The substitution effects on the geometry and the electronic structure of the ferrocene are systematically and comparatively studied using the density functional theory. It is found that -NH(2) and -OH substituents exert different influence on the geometry from -CH(3), -SiH(3), -PH(2), and -SH substituents. The topological analysis shows that all the C-C bonds in a-g are typical opened-shell interactions while the Fe-C bonds are typical closed-shell interactions. NBO analysis indicates that the cooperated interaction of d --> pi* and feedback pi --> d + 4s enhances the Fe-ligand interaction. The energy partitioning analysis demonstrates that the substituents with the second row elements lead to stronger iron-ligand interactions than those with the third row elements. The molecular electrostatic potential predicts that the electrophiles are expected to attack preferably the N, O, P, or S atoms in Fer-NH(2), Fer-OH, Fer-PH(2), and Fer-SH, and attack the ring C atoms in Fer-SiH(3) and Fer-CH(3). In turn, the nucleophiles are supposed to interact predominantly by attacking the hydrogen atoms. The simulated theoretical excitation spectra show that the maximum absorption peaks are red-shifted when the substituents going from second row elements to the third row elements.
authors.affiliation: College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150080, People's Republic of China.
authors.forename: Guiling
authors.initials: G
authors.lastname: Zhang
authors.forename: Hui
authors.initials: H
authors.lastname: Zhang
authors.forename: Miao
authors.initials: M
authors.lastname: Sun
authors.forename: Yanhong
authors.initials: Y
authors.lastname: Liu
authors.forename: Xiaohong
authors.initials: X
authors.lastname: Pang
authors.forename: Xiaoyang
authors.initials: X
authors.lastname: Yu
authors.forename: Bo
authors.initials: B
authors.lastname: Liu
authors.forename: Zesheng
authors.initials: Z
authors.lastname: Li