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Substitution effect on the geometry and electronic structure of the ferrocene
Author(s) -
Zhang Guiling,
Zhang Hui,
Sun Miao,
Liu Yanhong,
Pang Xiaohong,
Yu Xiaoyang,
Liu Bo,
Li Zesheng
Publication year - 2007
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20629
Subject(s) - chemistry , natural bond orbital , ferrocene , ligand (biochemistry) , crystallography , ring (chemistry) , electrophile , density functional theory , substitution reaction , hydrogen bond , open shell , atoms in molecules , computational chemistry , geometry , molecule , catalysis , electrochemistry , medicinal chemistry , organic chemistry , mathematics , biochemistry , receptor , electrode
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 CC bonds in a – g are typical opened‐shell interactions while the FeC bonds are typical closed‐shell interactions. NBO analysis indicates that the cooperated interaction of d → π* and feedback π → 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 FerNH 2 , FerOH, FerPH 2 , and FerSH, and attack the ring C atoms in FerSiH 3 and FerCH 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. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007