A DFT study on exohedral metallofullerenes: Structural and electronic properties

Fullerenes Nanotubes and Carbon Nanostructures

Volumn 17, Issue 5, 2009, Pages 457-475

  Loboda, Oleksandr ^a  

^a DUMANSKII INSTITUTE OF COLLOID AND WATER CHEMISTRY   (Ukraine)

Author keywords

B3LYP methods; CDA; Exohedral metallofullerenes; OLYP

Indexed keywords

B3LYP METHODS; BACK-DONATION; BOND DISSOCIATION ENERGIES; BOND STRENGTH; BONDING MODES; CDA; CHARGE DECOMPOSITION ANALYSIS; COORDINATION ENERGIES; DFT STUDY; EXOHEDRAL METALLOFULLERENES; FULLERENE CAGES; METAL ATOMS; METALLOFULLERENES; OLYP; OUTER SURFACE; QUANTITATIVE ESTIMATES; SIX-MEMBERED RINGS; STABLE STRUCTURES; TRANSITION METAL ATOMS;

ATOMS; CAGES (MINE HOISTS); CHEMICAL BONDS; COORDINATION REACTIONS; DENSITY FUNCTIONAL THEORY; ELECTRONIC PROPERTIES; ETHYLENE; PLATINUM; TRANSITION METALS;

FULLERENES;

EID: 70349757054     PISSN: 1536383X     EISSN: 15364046     Source Type: Journal    
DOI: 10.1080/15363830903008141     Document Type: Article

References (54)

1. Sulman, E., Matveeva, V., Semagina, N., Yanov, I., Bashilov, V., and Sokolov, V. (1999) Catalytic hydrogenation of acetylenic alcohols using palladium complex of fullerene C60. J. Mol. Cat., 146: 257.
2. Claridge, J., Douthwaite, R., and Green, M. (1994) Studies on a new catalyst for the hydroformylation of alkenes using C60 as a ligand. J. Mol. Catal., 89: 113.
3. Nagashima, H., Nakaoka, A., Tajima, S., Saito, Y., and Itoh, K. (1992) Catalytic-hydrogenation of olefins and acetylenes over C60Pdn. Chem. Lett., 21: 1361.
4. Nagashima, H., Kato, Y., Yamaguchi, H., Kimura, E., Kawanishi, T., Kato, M., Saito, Y., Haga, M., and Itoh, K. (1994) Synthesis and reactions of organoplatinum compounds of C60,C60Ptn. Chem. Lett., 7: 1207.
5. Wohlers, M., Herzog, B., Belz, T., Bauer, A, Braun, T., Ruhle, T., and Schlogl, R. (1996) Ruthenium-C60 compounds: Properties and catalytic potential. Synthetic Metals, 77: 55.
6. Braun, T., Wohlers, M., Belz, T., Nowitzke, G., Wormann, G., Uchida, Y., Pfander, N., and Schlogl, R. (1997) Fullerene-based ruthenium catalysts: A novel approach for anchoring metal to carbonaceous supports. 1. Structure. Cat. Lett., 43: 167.
7. Fagan, P., Calabrese, J., and Malone, B. (1991) The Chemical Nature of Buckminsterfullerene (C60) and the Characterization of a Platinum. Science, 252: 1160.
8. Fagan, P., Calabrese, J., and Malone, B. (1992) Metal-complexes of buckminsterfullerene (C60). Acc. Chem. Res., 25: 134.
9. Bashilov, V., Petrovskii, P., Sokolov, V., Lindeman, S., Guzey, I., and Struchkov, Y. (1993) Synthesis, crystal, and molecular-structure of the palladium(0)-fullerene derivative (eta-2-C60)Pd(PPH3)2. Organometallics,12: 991.
10. Dresselhaus, M., Dresselhaus, G., and Eklund, P. (1996) Science of Fullerenes and Carbon Nanotubes. Science of Fullerenes and Carbon Nanotubes, Academic Press, Inc.: San Diego.
11. Lerke, S.A., Evans, D.H., and Fagan, P.J. (1992) Electrochemical studies on metal derivatives of buckminsterfullerene (C60). J. Am. Chem. Soc., 114: 7807.
12. Fagan, P.J., Calabrese, J.C., and Malone, B. (1991) A multiply-substituted buckminsterfullerene (C60) with an octahedral array of platinum atoms. J. Am. Chem. Soc., 113: 9408.
13. Talyzin, A.V. and Jansson, U. (2003) A comparative Raman study of some tran-sition metal fullerides. Thin Solid Films, 429: 96.
14. Fujimoto, H., Nakao, Y., and Fukui, K. (1993) Orbital interactions in sizable systems - chemical bondings and regioselectivities in C60- transition-metal complexes. J. Mol. Struc., 300: 425.
15. Lichtenberger, D., Wright, L., Gruhn, N., and Rempe, M. (1994) Electronic- structure of exohedral interactions between C60 and transition metals. J. Organometal. Chem., 478: 213.
16. Andriotis, A. and Menon, M. (1999) Geometry and bonding in small (C60)mNin clusters. Phys. Rev., 60: 4521.
17. Alemany, M., Dieguez, O., Rey, C., and Gallego, L. (2001) A density functional study of the structures and electronic properties of C59Ni and C60Ni clusters. J. Chem. Phys., 114: 9371.
18. Handy, N. and Cohen, A. (2001) Left-right correlation energy. J. Mol Phys, 99: 403.
19. Dunning, T.H. Jr. (1970) Gaussian basis functions for use in molecular calculations. 1. Contraction of (9s5p) atomic basis sets for first-row atoms. J. Chem. Phys., 53: 2823.
20. Dunning, T. and Hay, P. (1977) In Methods of Electronic Structure Theory, vol.3, Schaeffer, H. (ed.), Plenum Press: New York.
21. Magnusson, E. and Schaefer, H.S. III (1985) Multiple d-type basis functions for molecules containing 2nd row atoms. J. Chem. Phys., 83: 5721.
22. Dolg, M., Wedig, U., Stoll, H., and Preuss, H. (1987) Energy-adjusted ab initio pseudopotentials for the 1st-row transition elements. J. Chem. Phys., 86: 866.
23. Andrae, D., Haeussermann, U., Dolg, M., and Stoll, H. (1990) Energy- adjusted ab initio pseudopotentials for the second and third row transition elements. Theor. Chim. Acta, 77: 123.
24. Becke, A. (1993) Density functional thermochemistry. 3. The role of exact exchange. J. Chem. Phys., 98: 5648.
25. Boys, S. and Bernardi, F. (1970) Calculation of small molecular interactions by differences of separate total energies - some procedures with reduced errors. Mol. Phys., 19: 553.
26. Koch, W. and Holthausen, M. (2000) A Chemist's Guide to Density Functional Theory, Wiley-VCH: Weinheim.
27. Hay, P. (1977) Gaussian basis sets for molecular calculations -representation of 3d orbitals in transition metal atoms. J. Chem. Phys., 66: 4377.
28. Moore, C. (1958) Atomic Energy Levels. Volume III, NBS: Washington, DC.
29. Glendening, E., Reed, A., Carpenter, J., and Weinhold, F. (2001) NBO Version 3.1.
30. Dapprich, S. and Frenking, G. (1995) Investigation of donor-acceptor interactions a charge decomposition analysis using fragment molecular-orbitals. J. Phys. Chem., 99: 9352.
31. Gorelsky, S.I. (1997) AOMix: Program for Molecular Orbital Analysis, York University: Toronto, http://www.sg-chem.net/
32. Gorelsky, S. and Lever, A. (2001) Electronic structure and spectral, of ruthenium diimine complexes by density functional theory and INDO/S. Comparison of the two methods. J. Organomet. Chem., 635: 187.
33. Hedberg, K., Hedberg, L., Bethune, D., Brown, C., Dorn, H., Johnson, R., and de Vries, M. (1991) Bond lengths in free molecules of buckminsterfuller- ene, C60, from gas-phase electron-diffraction. Science, 254: 410.
34. Nunzi, F., Sgamellotti, A., Re, N., and Floriani, C. (2000) A density functional study of C60 transition metal complexes. Organometallics, 19: 1628.
35. 60). J. Phys. Chem., 109: 8055.
36. 3)(2)}(n) (x=60, 70, 84; n=1-6). Inorg. Chem., 43: 6815.
37. 44) (M-Fe,Ru,Os). Inorg. Chem., 34: 3245.
38. 60 - confirmation of the soccer ball framework. Science, 252: 312.
39. Ward, M., Fagan, P., and Calabrese, J. (1989) Electrostatic structural enforcement in low-dimensional solids -synthesis, structure, and electronic properties of polycationic ruthenium complexes with polycyanoanions. J. Am. Chem. Soc., 111: 1719.
40. 60 as predicted by 2nd-order (MP2) perturbation theory. Chem. Phys. Lett., 181: 497.
41. 4) - the effect of alkene pyramidalization on internal rotation and alkene binding energies. J. Am. Chem. Soc., 113: 1912.
42. Blomberg, M., Siegbahn, P., and Svensson, M. (1992) Theoretical study of the binding of ethylene to 2nd-row transition metal atoms. J. Phys. Chem., 96: 9794.
43. Gates, B. (1992) Catalytic Chemistry, John Wiley Inc.: New York.
44. Blomberg, M., Siegbahn, P., Nagashima, U., and Wennerberg, J. (1991) Theoretical study of the activation of alkane C-H and C-C bonds by different transition metals. J. Am. Chem. Soc., 113: 424.
45. Visscher, L. and Dyall, K. (1997) Dirac-Fock atomic electronic structure calculations using different nuclear charge distributions. Atomic Data and Nuclear Data Tables, 67: 207.
46. Weisshaar, J. (1993) Reactions of gas-phase transition metal atoms with small hydrocarbons. ACS Symposium Series, 530: 208.
47. Ritter, D. and Weisshaar, J. (1990) Reactivity of neutral Fe, Co, Ni, and Cu atoms with linear alkanes and alkenes in the gas phase. J. Am. Chem. Soc., 112: 6425.
48. 4) complex -a CASSCF-CI study. J. Phys. Chem., 89: 2180.
49. Siegbahn, P. and Brandemark, U. (1986) Orientational preference of 2 ethylene ligands bound to a nickel atom. Theor. Chim. Acta, 69: 119.
50. Chatt, J. and Duncanson, L. (1953) Olefin coordination compounds 3. Infrared spectra and structure-attempted preparation ofacetylene complexes. J. Chem. Soc., 2939. 10.1039/JR953002939
51. Dewar, M. (1951) A review of the π-complex theory. Bull. Soc. Chim. Fr., 18: 71.
52. 2. Organometallics, 22: 2758.
53. 4. Can. J. Chem., 50: 912.
54. In order to fulfil the requirement of AOMIX program "Number of canonical orbitals = number of basis functions" and to avoid linear dependency problems, we had to run B3LYP single point calculations without diffuse basis function on carbon. Obtained BDE are very similar to the previous and does not differ from them by more than 0.3 kcal/mol.