Abstract
The conformational stability of 4, 4′ disubstituted HC60–C60R and RC60–C60R dimers were calculated at ONIOM approach (AM1:B3LYP/6-31+G**) and density functional theory (B3LYP/6-31G**). The new evidences for stability and rotational energy barriers of these dimers were obtained by natural bond orbital, natural steric and molecular orbital analyses. Based on B3LYP/6-31G** calculations, except for RC60–C60R (R = hydrogen, tert-butyl and trimethylsilyl) where gauche is the most stable conformer, trans is a global energy minimum. The greater stability of the gauche conformer of HC60–C60H over trans is the result of hyperconjugation, which dominates the instability caused by the steric effect. By increasing the size of the substituent of HC60–C60R dimers, the trans becomes sterically unstable but the hyperconjugation of bulky substituents dominates (the trans is global energy minimum). The hyperconjugation stability of RC60–C60R dimers dominates until R = iso-propyl (higher stability of trans). In the case of bulky tert-butyl and trimethylsilyl substituents, the steric energy of trans is large and overweighs the hyperconjugation effect. This favors gauche as the most stable conformer. The calculated rotational energy barrier for HC60–C60R and RC60–C60R dimers is less than 7.3 and more than 10 kcal/mol, respectively (depending on substitution).
Similar content being viewed by others
References
G. Bringmann, A.J.P. Mortimer, P.A. Keller, M.J. Gresser, J. Garner, M. Breuning, Angew. Chem. Int. Ed. 44, 5384 (2005)
L. Pu, Chem. Rev. 98, 2405 (1998)
A. Suzuki, J. Organomet. Chem. 576, 147 (1999)
B. Freedman, C. Xiaolin, L.A. Nafie, B.M. Kalbermatter, L. Anthony, A.J. Rippert, Helv. Chim. Acta 86, 3141 (2003)
A.S. Cooke, M.M. Harris, J. Chem. Soc. 2365 (1963)
F.A. Carey, R.J. Sundberg, Advanced organic chemistry part A: structure and mechanisms (Springer, 2007)
J. Poater, M. Solà, F.M. Bickelhaupt, Chem. Eur. J. 12, 2889 (2006)
A. Almenningen, O. Bastiansen, L. Fernholt, B.N. Cyvin, S.J. Cyvin, S. Samdal, J. Mol. Struct. 128, 59 (1985)
L. Meca, D. Reha, Z. Havlas, J. Org. Chem. 68, 5677 (2003)
O. Lafon, P. Lesot, C.A. Fan, H.B. Kagan, Chem. Eur. J. 13, 3772 (2007)
D. Nori-shargh, S. Asadzadeh, F.R. Ghanizadeh, F. Deyhimi, M.M. Amini, S. Jameh-Bozorghi, J. Mol. Struct. Theochem. 717, 41 (2005)
R. Fortrie, H. Chermette, J. Chem. Theory Comput. 3, 852 (2007)
L. Lunazzi, M. Mancinelli, A. Mazzanti, J. Org. Chem. 73, 2198 (2008)
D. Eisenberg, A.S. Filatov, E.A. Jackson, M. Rabinovitz, M.A. Petrukhina, L.T. Scott, R. Shenhar, J. Org. Chem. 73, 6073 (2008)
K. Komatsu, G.W. Wang, Y. Murata, T. Tanaka, K. Fujiwara, K. Yamamoto, M. Saunders, J. Org. Chem. 63, 9358 (1998)
A. Bihlmeier, C.C.M. Samson, W. Klopper, Chem. Phys. Chem. 6, 2625 (2005)
H. Ueno, S. Osawa, E. Osawa, K. Takeuchi, Fullerene Sci. Technol. 6, 319 (1998)
K.H. Lee, H.M. Eun, S.S. Park, K.W. Jung, S.M. Lee, Y.H. Lee, E. Osawa, J. Phys. Chem. B 104, 7038 (2000)
N. Matsuzawa, M. Ata, D.A. Dixon, G. Fitzgerald, J. Phys. Chem. 98, 2555 (1994)
N. Kaur, S. Gupta, K. Dharamvir, V.K. Jindal, Carbon 46, 349 (2008)
S.G. Stepanian, V.A. Karachevtsev, A.M. Plokhotnichenko, L. Adamowicz, A.M. Rao, J. Phys. Chem. B 110, 15769 (2006)
S. Tsukamoto, T. Nakayama, M. Aono, Carbon 45, 1261 (2007)
G. Wang, Y. Li, Y. Huang, J. Phys. Chem. B 109, 10957 (2005)
K. Komatsu, K. Fujiwara, T. Tanaka, Y. Murata, Carbon 38, 1529 (2000)
G.W. Wang, K. Komatsu, Y. Murata, M. Shiro, Nature 387, 583 (1997)
A.A. Shvartsburg, R.R. Hudgins, R. Gutierrez, G. Jungnickel, T. Frauenheim, K.A. Jackson, M.F. Jarrold, J. Phys. Chem. A 103, 5275 (1999)
E.A. Halevi, J. Phys. Org. Chem. 15, 519 (2002)
S. Patchkovskii, W. Thiel, J. Am. Chem. Soc. 120, 556 (1998)
M.V. Diudea, C.L. Nagy, O. Ursu, T.S. Balaban, Fullerenes Nanotubes Carbon Nanostr 11, 245 (2003)
N. Kaur, K. Dharamvir, V.K. Jindal, Chem. Phys. 344, 176 (2008)
M. Koshinol, Y. Niimi, E. Nakamura, H. Kataura, T. Okazaki, K. Suenaga, S. Iijima, Nature Chemistry 2, 117 (2010)
Y.H. Kim, I.H. Lee, K.J. Chang, S. Lee, Phys. Rev. Lett. 90, 065501 (2003)
W. Andreoni, Annu. Rev. Phys. Chem. 49, 405 (1998)
M. Menon, K.R. Subbaswamy, M. Sawtarie, Phys. Rev. B 49, 13966 (1994)
G.B. Adams, J.B. Page, O.F. Sankey, M. O’Keeffe, Phys. Rev. B 50, 17471 (1994)
F.L. Liu, X.X. Zhao, J. Mol. Struct. Theochem. 804, 117 (2007)
A. Lazar, P.R. Surjan, J. Mol. Struct. Theochem. 501–502, 369 (2000)
S. Lebedkin, S. Ballenweg, J. Gross, R. Taylor, W. Kratschmer, Tetrahedron Lett. 36, 4971 (1995)
A.B. Smith, H. Tokuyama, R.M. Strongin, G.T. Furst, W.J. Romanow, J. Am. Chem. Soc. 117, 9359 (1995)
X.B. Wang, K. Matheis, I.N. Ioffe, A.A. Goryunkov, J. Yang, M.M. Kappes, L.S. Wang, J. Chem. Phys. 128, 114307 (2008)
A. Gromov, S. Lebedkin, S. Ballenweg, A.G. Avent, R. Taylor, W. Kratschmer, Chem. Commun. 2, 209 (1997)
H. Shimotani, N. Dragoe, K. Kitazawa, J. Phys. Chem. A. 105, 4980 (2001)
X. Gao, Y. Zhao, H. Yuan, Z. Chen, Z. Chai, Chem. Phys. Lett. 418, 24 (2006)
J. Osterodt, F. Vögtle, Chem. Commun. 4, 547 (1996)
T.S. Fabre, W.D. Treleaven, T.D. McCarley, C.L. Newton, R.M. Landry, M.C. Saraiva, R.M. Strongin, J. Org. Chem. 63, 3522 (1998)
N. Dragoe, S. Tanibayashi, K. Nakahara, S. Nakao, H. Shimotani, L. Xiao, K. Kitazawa, Y. Achiba, K. Kikuchi, K. Nojima, Chem. Commun. 1, 85 (1999)
N. Dragoe, H. Shimotani, M. Hayashi, K. Saigo, A. de Bettencourt-Dias, A.L. Balch, Y. Miyake, Y. Achiba, K. Kitazawa, J. Org. Chem. 65, 3269 (2000)
C.N.R. Rao, A. Govindaraj, H.N. Aiyer, R. Seshadri, J. Phys. Chem. 99, 16814 (1995)
J.E. Fischer, Science 264, 1548 (1994)
C. Wang, G. Zhi-Xin, S. Fu, W. Wu, Z. Daoben, Prog. Polym. Sci. 29, 1079 (2004)
M. Springborg, Phys. Rev. B 52, 2935 (1995)
P.R. Surjan, A. Lazar, M. Kallay, Phys. Rev. B 58, 3490 (1998)
S.C. Benjamin, A. Ardavan, G.A.D. Briggs, D.A. Britz, D. Gunlycke, J. Jefferson, M.A.G. Jones, D.F. Leigh, B.W. Lovett, A.N. Khlobystov, S.A. Lyon, J.J.L. Morton, K. Porfyrakis, M.R. Sambrook, A.M. Tyryshkin, J. Phys. Condens. Matter. 18, S867 (2006)
J.L. Segura, N. Martín, Chem. Soc. Rev. 29, 13 (2000)
J.R. Morton, F. Negri, K.F. Preston, Acc. Chem. Res. 31, 63 (1998)
J.R. Morton, K.F. Preston, P.J. Krusic, S.A. Hill, E. Wasserman, J. Phys. Chem. 96, 3576 (1992)
J.R. Morton, K.F. Preston, P.J. Krusic, S.A. Hill, E. Wasserman, J. Am. Chem. Soc. 114, 5454 (1992)
J.R. Morton, K.F. Preston, P.J. Krusic, S.A. Hill, E. Wasserman, J. Chem. Soc. Perkin Trans. 2, 1425 (1992)
P.J. Krusic, D.C. Roe, E. Johnston, J.R. Morton, K.F. Preston, J. Phys. Chem. 97, 1736 (1993)
J.R. Morton, F. Negri, K.F. Preston, G. Ruel, J. Phys. Chem. 99, 10114 (1995)
P.J. Fagan, P.J. Krusic, C.N. McEwen, J. Lazar, D.H. Parker, N. Herron, E. Wasserman, Science 262, 404 (1993)
J.R. Morton, K.F. Preston, J. Phys. Chem. 98, 4993 (1994)
P. Zhou, Z.H. Dong, A.M. Rao, P.C. Eklund, Chem. Phys. Lett. 211, 337 (1993)
Y. Wang, J.M. Holden, Z.H. Dong, X.X. Bi, P.C. Eklund, Chem. Phys. Lett. 211, 341 (1993)
J.R. Morton, K.F. Preston, P.J. Krusic, L.B. Knight Jr., Chem. Phys. Lett. 204, 481 (1993)
J.A. Howard, Chem. Phys. Lett. 203, 540 (1993)
P.J. Fagan, P.J. Krusic, D.H. Evans, S.A. Lerke, E. Johnston, J. Am. Chem. Soc. 114, 9697 (1992)
T. Tanaka, K. Komatsu, J. Chem. Soc. Perkin Trans. 1, 1671 (1999)
D.V. Konarev, S.S. Khasanov, A. Otsuka, G. Saito, J. Am. Chem. Soc. 124, 8520 (2002)
D.V. Konarev, R.N. Lyubovskaya, S.S. Khasanov, A. Otsuka, G. Saito, Mol. Cryst. Liq. Cryst. 468, 227 (2007)
D.V. Konarev, S.S. Khasanov, G. Saito, A. Otsuka, Y. Yoshida, R.N. Lyubovskaya, J. Am. Chem. Soc. 125, 10074 (2003)
A. Hönnerscheid, R. Dinnebier, M. Jansen, Acta Cryst. B 58, 482 (2002)
K. Komatsu, N. Takimoto, Y. Murata, T.S.M. Wan, T. Wong, Tetrahedron Lett. 37, 6153 (1996)
P. Timmerman, L.E. Witschel, F. Diederich, C. Boudon, J.P. Gisselbrecht, M. Gross, Helv. Chim. Acta 79, 6 (1996)
H. Hauke, A. Hirsch, Tetrahedron 57, 3697 (2001)
M.M. Roubelakis, G.C. Vougioukalakis, L.C. Nye, T. Drewello, M. Orfanopoulos, Tetrahedron 66, 9363 (2010)
R. Kumashiro, K. Tanigaki, H. Ohashi, N. Tagmatarchis, H. Kato, H. Shinohara, T. Akasaka, K. Kato, S. Aoyagi, S. Kimura, M. Takata, Appl. Phys. Lett. 84, 2154 (2004)
F. Simon, D. Aron, N. Tagmatarchis, S. Garaj, L. Forro, K. Prassides, J. Phys. Chem. A 103, 6969 (1999)
J.C. Hummelen, B. Knight, J. Pavlovich, R. González, F. Wudl, Science 269, 1554 (1995)
S. Osawa, E. Osawa, M. Harada, J. Org. Chem. 61, 257 (1996)
K.H. Lee, S.S. Park, Y. Suh, T. Yamabe, E. Osawa, H.P. Lüthi, P. Gutta, C.H. Lee, J. Am. Chem. Soc. 123, 11085 (2001)
C. Lee, S.S. Park, W.R. Lee, K.H. Lee, Bull. Korean Chem. Soc. 31, 457 (2010)
S. Osuna, J. Morera, M. Cases, K. Morokuma, M. Sola, J. Phys. Chem. A 113, 9721 (2009)
M. Izquierdo, S. Osuna, S. Filippone, A. Martin-Domenech, M. Sola, N. Martin, J. Org. Chem. 74, 6253 (2009)
M. Izquierdo, S. Osuna, S. Filippone, A. Martin-Domenech, M. Sola, N. Martin, J. Org. Chem. 74, 1480 (2009)
S. Irle, Y. Rubin, K. Morokuma, J. Phys. Chem. A 106, 680 (2002)
Y. Mo, J. Gao, Acc. Chem. Res. 40, 113 (2007)
Y. Mo, Nature Chemistry 2, 666 (2010)
E.J. Cocinero, P. Çarçabal, T.D. Vaden, J.P. Simons, B.G. Davis, Nature 469, 76 (2011)
D.Y. Buissonneaud, T. van Mourik, D. O’Hagan, Tetrahedron 66, 2196 (2010)
H.A. Dabbagh, M. Zamani, H. Farrokhpour, M.H. Habibi, K. Barati, J. Mol. Struct. 983, 169 (2010)
F. Maseras, K. Morokuma, J. Comp. Chem. 16, 1170 (1995)
M. Svensson, S. Humbel, R.D.J. Froese, T. Matsubara, S. Sieber, K. Morokuma, J. Phys. Chem. 100, 19357 (1996)
S. Dapprich, I. Komáromi, K.S. Byun, K. Morokuma, M.J. Frisch, J. Mol. Struct. Theochem. 462, 1 (1999)
M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision B.02 (Gaussian, Inc., Pittsburgh PA, 2003)
E.D. Glendening, J.K. Badenhoop, A.E. Reed, J.E. Carpenter, J.A. Bohmann, C.M. Morales, F. Weinhold, NBO 5.0 (Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2001)
F. Weinhold, NBO 5.0/5.G Program Manual, Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706
J.K. Badenhoop, F. Weinhold, J. Chem. Phys. 107, 5406 (1997)
J.K. Badenhoop, F. Weinhold, J. Chem. Phys. 107, 5422 (1997)
J.K. Badenhoop, F. Weinhold, Int. J. Quantum Chem. 72, 269 (1999)
Acknowledgments
We would like to thank the Isfahan University of Technology (IUT) Research Council for financial support. We thank the Supercomputing Centre of Isfahan University of Technology and Dr. M. Ashrafizaheh for their kindly support in performing some of the computations. Also, the authors are grateful to Dr. A.R. Najafi (Yasouj University) for valuable discussions.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Dabbagh, H.A., Zamani, M. & Mortaji, H. Conformational stability and rotational energy barrier of RC60–C60R dimers: hyperconjugation versus steric effect. J IRAN CHEM SOC 9, 205–223 (2012). https://doi.org/10.1007/s13738-011-0042-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13738-011-0042-7