Abstract
Conformational energies of monomeric (1,2-dimethoxyethane, DME) and trimeric (triglyme) model compounds of poly(ethylene oxide) have been evaluated by accurate ab initio molecular orbital (MO) calculations at the MP2/6-311++G(3df, 3pd)//HF/6-31G(d) level. The first-order interaction energies (Eσ’s) for gauche states around the C–C bonds of DME and the terminal repeating unit of triglyme are ca. +0.1 kcal mol−1, whereas the central unit of triglyme has a slightly negative Eσ value of ca. −0.1 kcal mol−1. For the C–C bond conformations of triglyme, the MO calculations exactly agree with NMR observations using a nonpolar solvent of cyclohexane-d12. The attractive gauche effect of the ethylene oxides has been shown to exist independently of intramolecular (C–H)···O hydrogen bonds.
Similar content being viewed by others
Article PDF
References
E. Juaristi, “Introduction to Stereochemistry and Conformational Analysis,” Wiley & Sons, New York, 1991, chap. 18.
E. Juaristi and G. Cuevas, “The Anomeric Effect,” CRC Press, Boca Raton, FL, 1995, chap. 4.
Y. Sasanuma, H. Ohta, I. Touma, H. Matoba, Y. Hayashi, and A. Kaito, Macromolecules, 35, 3748 (2002).
J. E. Mark and P. J. Flory, J. Am. Chem. Soc., 87, 1415 (1965).
P. J. Flory, “Statistical Mechanics of Chain Molecules,” Wiley & Sons, New York, 1969.
A. Abe and J. E. Mark, J. Am. Chem. Soc., 98, 6468 (1976).
K. Tasaki and A. Abe, Polym. J., 17, 641 (1985).
D. T. Baldwin, W. L. Mattice, and R. D. Gandour, J. Comput. Chem., 5, 241 (1984).
A. Abe, H. Furuya, M. K. Mitra, and T. Hiejima, Comput. Theor. Polym. Sci., 8, 253 (1998).
G. D. Smith, D. Bedrov, and O. Borodin, J. Am. Chem. Soc., 122, 9548 (2000).
A. E. Reed, L. A. Curtiss, and F. Weinhold, Chem. Rev., 88, 899 (1988).
H. Tadokoro, Y. Chatani, T. Yoshihara, S. Tahara, and S. Murahashi, Makromol. Chem., 73, 109 (1964).
Y. Takahashi and H. Tadokoro, Macromolecules, 6, 672 (1973).
Y. Takahashi, I. Sumita, and H. Tadokoro, J. Polym. Sci., Polym. Phys. Ed., 11, 2113 (1973).
K. Tashiro and H. Tadokoro, Rep. Prog. Polym. Phys. Jpn., 21, 417 (1978).
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, V. Bakken, 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, and J. A. Pople, Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford CT, 2004.
J. A. Pople, A. P. Scott, M. W. Wong, and L. Radom, Isr. J. Chem., 33, 345 (1993).
W. L. Mattice and U. W. Suter, “Conformational Theory of Large Molecules: The Rotational Isomeric State Model in Macromolecular Systems,” Wiley & Sons, New York, 1994.
P. H. M. Budzelaar, “gNMR, version 5.0,” IvorySoft & Adept Scientific plc, Letchworth, U.K., 2004.
K. Inomata and A. Abe, J. Phys. Chem., 96, 7934 (1992).
A. Abe, R. L. Jernigan, and P. J. Flory, J. Am. Chem. Soc., 88, 631 (1966).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sasanuma, Y., Sugita, K. The Attractive Gauche Effect of Ethylene Oxides. Polym J 38, 983–988 (2006). https://doi.org/10.1295/polymj.PJ2006018
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1295/polymj.PJ2006018
Keywords
This article is cited by
-
Solution properties of poly(N-methylethylene imine), a highly hydrophilic polycation
Polymer Journal (2016)
-
Nano-network with dual temperature and pH responsiveness based on copolymers of 2-hydroxyethyl methacrylate with 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane
Journal of Nanoparticle Research (2011)
-
Conformational analysis for hydrated ethylene oxide oligomer models by quantum chemical calculations
Polymer Bulletin (2009)
-
Conformational analysis of ethylene oxide and ethylene imine oligomers by quantum chemical calculations: solvent effects
Polymer Bulletin (2008)