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A theoretical study of fullerene–ferrocene hybrids
Author(s) -
Kang Hong Seok
Publication year - 2006
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.20539
Subject(s) - ferrocene , chemistry , ring (chemistry) , homo/lumo , atom (system on chip) , density functional theory , cyclopentadienyl complex , crystallography , isomerization , fullerene , computational chemistry , electrochemistry , molecule , organic chemistry , catalysis , electrode , computer science , embedded system
Abstract Using density functional theory within the generalized gradient approximation, I analyzed the electronic structure of a C 60 –ferrocene hybrid [= C 60 *FeCp] around HOMO in comparison with that of ferrocene, where C 60 *and Cp denote C 60 (CH 3 ) 5 and a cyclopentadienyl ring. HOMO–LUMO gap is significantly smaller than that of ferrocene because of the intervention of π(C 60 * ) states below LUMO. In addition, geometrical and electronic structures of N@C 60 *FeCp are also investigated. I find that there are two isomers with the energy difference of 0.13 eV. In one of the two, the encased nitrogen atom is located at the center of the fullerene cage. The Fe atom is η 5 ‐coordinated to both Cp and R*, where R* is a five‐membered ring of C 60 *cage. On the other hand, the atom is coordinated to R* with η 4 ‐hapticity, and the nitrogen atom is bonded to a carbon atom of the R* ring in the other isomer. Upon the isomerization between the two isomers, there occurs a partial transfer of spin density between the nitrogen and Fe atoms as well as the creation and breaking of a CN bond. © 2006 Wiley Periodicals, Inc. J Comput Chem 28: 594–600, 2007