A theoretical study on fullerene‐dizincocene hybrids

Using the density functional theory, we investigated the possible formation of fullerene‐dizincocene hybrids, specifically C60*‐Zn‐Zn‐Cp*, C60*‐Zn‐Zn‐C60*, C70*‐Zn‐Zn‐Cp*, and C70*‐Zn‐Zn‐C70*, where C60*, Cp*, and C70* represent C60(CH3)5, C5(CH3)5, and C70(CH3)5 radicals. Our calculation shows that these hybrids have HOMO‐LUMO gaps which are larger than has been experimentally identified for C60*‐Fe‐Cp. In addition, the strength of the ZnZn bonds is similar to that in Cp*‐Zn‐Zn‐Cp* which was also synthesized recently. Furthermore, heterohybrids, C60*‐Zn‐Zn‐Cp* and C70*‐Zn‐Zn‐Cp* are expected to exist in equilibria with homohybrids, C60*‐Zn‐Zn‐C60* and C70*‐Zn‐Zn‐C70*, in which heterohybrids are much more favored. On the other hand, another hybrid involving Sc3N@C68 as a fullerene unit is not highly probable. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009

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

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

[3]  Eric Rivard,et al.  Synthesis, structural characterization, and spectroscopy of the cadmium-cadmium bonded molecular species Ar'CdCdAr' (Ar' = C6H3-2,6-(C6H3-2,6-Pri2)2). , 2006, Journal of the American Chemical Society.

[4]  Agustín Galindo,et al.  Theoretical and synthetic studies on [Zn2(eta5-C5Me5)2]: analysis of the Zn-Zn bonding interaction. , 2005, Angewandte Chemie.

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

[6]  Hong Seok Kang,et al.  A theoretical study of fullerene–ferrocene hybrids , 2007, J. Comput. Chem..

[7]  Hong Seok Kang,et al.  Density functional study of chemical stability and nitrogen encapsulation of C48N12 and C58N12. , 2006, The journal of physical chemistry. A.

[8]  Kenneth B. Wiberg,et al.  Application of the pople-santry-segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane , 1968 .

[9]  Wei-Hai Fang,et al.  A combined DFT and CCSD(T) study on electronic structures and stability of the M2(η5-CpX)2 (M = Zn and Cd, CpX = C5Me5 and C5H5) complexes , 2005 .

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

[11]  J. W. Kress,et al.  Density functional theory investigation of decamethyldizincocene. , 2005, The journal of physical chemistry. A.

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

[13]  E. Gutiérrez‐Puebla,et al.  Decamethyldizincocene, a Stable Compound of Zn(I) with a Zn-Zn Bond , 2004, Science.

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

[15]  Eric Rivard,et al.  A zinc-zinc-bonded compound and its derivatives bridged by one or two hydrogen atoms: a new type of Zn-Zn bonding. , 2006, Angewandte Chemie.

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

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

[18]  Eiichi Nakamura,et al.  Synthesis and reactivity of Bucky ruthenocene Ru(η5-C60Me5)(η5-C5H5) , 2004 .

[19]  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.

[20]  Krishna K. Pandey.  Structure and energy decomposition analysis of metal–metal bonding in [PhM–MPh] and [ClM–MCl] (M = Zn, Cd, Hg) , 2007 .

[21]  Andreas M Köster,et al.  13C NMR pattern of Sc3N@C68. Structural assignment of the first fullerene with adjacent pentagons. , 2005, The journal of physical chemistry. A.

[22]  Gabriel Merino,et al.  Multimetallocenes. A Theoretical Study , 2007 .

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

[24]  Yaoming Xie,et al.  The dichotomy of dimetallocenes: coaxial versus perpendicular dimetal units in sandwich compounds. , 2005, Journal of the American Chemical Society.

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

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

[27]  Gernot Frenking,et al.  Bis(benzene)chromium Is a δ-Bonded Molecule and Ferrocene Is a π-Bonded Molecule† , 2003 .

[28]  M. Itkis,et al.  Chemistry of single-walled carbon nanotubes. , 2002, Accounts of chemical research.

[29]  Agustín Galindo,et al.  Zinc-zinc bonded zincocene structures. Synthesis and characterization of Zn2(eta5-C5Me5)2 and Zn2(eta5-C5Me4Et)2. , 2007, Journal of the American Chemical Society.

[30]  A. Grirrane,et al.  Cyclopentadienyl zincates: synthesis and X-ray studies of sodium and potassium salts of the [Zn(C5H5)3]- and [Zn2(C5H5)5]- ions. , 2007, Angewandte Chemie.

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

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

[33]  Henry F. Schaefer,et al.  Donor−Acceptor Sandwiches of Main-Group Elements , 2005 .

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

[35]  Krishna Pandey.  Energy analysis of metal–metal bonding in [RM–MR] (M = Zn, Cd, Hg; R = CH3, SiH3, GeH3, C5H5, C5Me5) , 2007 .

[36]  Hongyan Wang,et al.  On the chemistry of Zn-Zn bonds, RZn-ZnR (R = [{(2,6-Pri2C6H3)N(Me)C}2CH]): synthesis, structure, and computations. , 2005, Journal of the American Chemical Society.

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

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