A theoretical study of fullerene–ferrocene hybrids

Using density functional theory within the generalized gradient approximation, I analyzed the electronic structure of a C60–ferrocene hybrid [= C  60* FeCp] around HOMO in comparison with that of ferrocene, where C  60* and Cp denote C60(CH3)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 η5‐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 η4‐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 CN bond. © 2006 Wiley Periodicals, Inc. J Comput Chem 28: 594–600, 2007

[1]  Hong Seok Kang,et al.  Theoretical study of binding of metal-doped graphene sheet and carbon nanotubes with dioxin. , 2005, Journal of the American Chemical Society.

[2]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[3]  Kees Hummelen,et al.  Fullerenes and related structures , 1999 .

[4]  C. Corvaja,et al.  Synthesis and magnetic properties of N@C60 derivatives , 2006 .

[5]  Eiichi Nakamura,et al.  Synthesis of ferrocene/hydrofullerene hybrid and functionalized bucky ferrocenes. , 2003, Journal of the American Chemical Society.

[6]  Hong Seok Kang,et al.  Theoretical study of complexes of extended cyclopentadienyl ligands with zinc and cadmium. , 2005, The journal of physical chemistry. A.

[7]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[8]  Hong Seok Kang.  Density functional study of lithium-aromatic sandwich compounds and their crystals. , 2005, The journal of physical chemistry. A.

[9]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[10]  Hong Seok Kang.  Magnetic couplings in vanadium aromatic sandwich complexes and their crystals by using DFT methods. , 2005, The journal of physical chemistry. A.

[11]  Eiichi Nakamura,et al.  Synthesis and catalytic activity of rhodium diene complexes bearing indenyl-type fullerene η5-ligand , 2003 .

[12]  K. Lips,et al.  Atomic Nitrogen Encapsulated in Fullerenes: Realization of a Chemical Faraday Cage , 2000 .

[13]  L. Curtiss,et al.  Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint , 1988 .

[14]  Eiichi Nakamura,et al.  Bucky ferrocene and ruthenocene: serendipity and discoveries , 2004 .

[15]  K. Lips,et al.  Atomic Nitrogen Encapsulated in Fullerenes: Effects of Cage Variations , 1999 .

[16]  Hong Seok Kang,et al.  Theoretical study of endohedral C36 and its dimers. , 2006, The journal of physical chemistry. A.

[17]  G. Kresse,et al.  Ab initio molecular dynamics for liquid metals. , 1993 .

[18]  Hong Seok Kang,et al.  Theoretical study of boron nitride nanotubes with defects in nitrogen-rich synthesis. , 2006, The journal of physical chemistry. B.

[19]  Hideomi Koinuma,et al.  Photoinduced change in the Raman spectrum of buckyferrocene ((Fe(C 60(CH 3) 5)C 5H 5) , 2004 .

[20]  Hong Seok Kang,et al.  Theoretical study of main-group metal-borazine sandwich complexes. , 2005, The journal of physical chemistry. A.