Abstract
Monte Carlo statistical mechanics simulations have been used to study the complexation of disubstituted benzenes by Diederich’s octamethoxy tetraoxaparacyclophane host, 1. The calculations were carried out in the NPT ensemble at 25 °C and 1 atm in the presence of 768 water molecules. Relative free energies of binding were obtained for p-xylene, benzene, p-cresol, and hydroquinone from statistical perturbation theory. The computed preference of 2.8 ± 0.3 kcal/mol in DGb for binding p-xylene over hydroqinone compares well with the experimental result of 2.5 ± 0.3 kcal/mol. The computed results for benzene (2.0 ± 0.2 kcal/mol) and p-cresol (2.4 ± 0.2 kcal/mol) relative to p-xylene were predictions; however, the experimental data are now available and are lower by 1–2 kcal/mol. The computed structures for the complexes reveal interesting details. For example, hydroquinone protrudes somewhat from one side of the complex and participates in hydrogen bonds between one hydroxyl group and 1–2 water molecules and in an intracomplex hydrogen bond between the other hydroxyl group and ether oxygens. Benzene is predicted to be bound even more off-center, while p-cresol is centered and has an intracomplex hydrogen bond as in the case of hydroquinone.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
Reference
Lehn, J.-M. Ancrew. Chem., Int. Ed. Engl. 1988, 27, 89.
Cram, D. J. Ancrew. Chem., Int. Ed. Engl. 1988, 27, 1009.
Rebek, J., Jr. Acc. Chem. Res. 1990, 23, 399.
Diederich, F. Angew. Chem., Int. Ed. Engl. 1988, 27, 362.
Lehn, J.-M. Ancrew. Chem., Int. Ed. Engl. 1990, 29, 1304.
McCammon, J. Α.; Harvey, S. C. “Dynamics of Proteins and Nucleic Acids”; Cambridge Univ. Press: Cambridge, 1987.
van Gunsteren, W. F.; Berendsen, H. J. C. Angew Chem., Int. Ed. Engl. 1990, 29, 992.
Kollman, Ρ. Α.; Merz, Κ. M., Jr. Acc. Chem. Res. 1990, 23, 246.
Brooks, C. L., III; Karplus, M.; Pettitt, Β. M. Adv. Chem. Phys. 1988, 71, 1.
Lybrand, T. P.; McCainmon, J. A.; Wipff, G. Proc. Natl. Acad. Sci. USA 1986, 83, 833.
Mazor, M. H.; McCainmon, J. A.; Lybrand, T. P. J. Am. Chem. Soc. 1989, 111, 55.
Dang, L. X.; Kollman, P. A. J. Am. Chem. Soc. 1990, 112, 5716.
Grootenhuis, P. D. J.; Kollman, P. A.; Groenen, L. C.; Reinhoudt, D. N.; van Hummel, G. J.; Ugozzoli, F.; Andreetti, G. D. J. Am. Chem. Soc. 1990, 112, 4165.
Jorgensen, W. L. Aoc. Chem. Res. 1989, 22, 184.
Jorgensen, W. L. Chemtracts — Organic Chemistry 1991, 4, 91.
Jorgensen, W. L.; Boudon, S.; Nguyen, T. B. J. Am. Chem. Soc. 1989, 111, 755.
Ferguson, S. B.; Seward, Ε. M.; Diederich, F.; Sanford, E. M.; Chou, Α.; Inocencio-Szweda; Khobler, C. B. J. Org. Chem. 1988, 53, 5593.
Ferguson, S. B.; Sanford, E. M.; Seward, Ε. M.; Diederich, F. L. Am. Chem. Soc. 1991, 113, 5410.
Smithrud, D. B.; Wyman, T. B.; Diederich, F. J. Am. Chem. Soc. 1991, 113, 5420.
Jorgensen, W. L. BOSS, Version 3.1 1991, Yale University, New Haven, CT.
Weiner, S. J.; Kollman, P. Α.; Case, D. Α.; Singh, U. C.; Ghio, C.; Alagona, G.; Profeta, S., Jr.; Weiner, P. J. Am. Chem. Soc. 1984, 106, 765.
a) Jorgensen, W. L.; Tirado-Rives, J. J. Am. Chem. Soc. 1988, 110, 1657. (b) Jorgensen, W. L.; Briggs, J. M.; Contreras, M. L. J. Phys. Chem. 1990, 94, 1683. (c) Jorgensen, W. L.; Severance, D. L. J. Am. Chem. Soc. 1990, 112, 4768.
Zwanzig, R. W. J. Chem. Phys. 1953
Jorgensen, W. L.; Madura, J. D. Mol. Phvs. 1985, 56, 1381.
Nguyen, Τ. Β.; Jorgensen, W. L., to be published.
(a) Hine, J.; Mookerjee, P. K. J. Ora. Chem. 1975, 40, 292. (b) Ben-Nairn, Α.; Marcus, Y. J. Chem. Phvs. 1984, 81, 2016. (c) Riddick, J. A.; Bunger, W. B.; Sakano, T. K. “Organic Solvents: Physical Properties and Methods of Purification, 4th Edition”; Wiley: New York, 1986. (d) Kuyper, L. F.; Hunter, R. N.; Ashton, D.; Merz, Κ. Μ., Jr.; Kollman, P. A. J. Fhys. Chem. 1991, 95, 6661.
(a) Hine, J.; Mookerjee, P. K. J. Ora. Chem. 1975, 40, 292. (b) Ben-Nairn, Α.; Marcus, Y. J. Chem. Phvs. 1984, 81, 2016. (c) Riddick, J. A.; Bunger, W. B.; Sakano, T. K. “Organic Solvents: Physical Properties and Methods of Purification, 4th Edition”; Wiley: New York, 1986. (d) Kuyper, L. F.; Hunter, R. N.; Ashton, D.; Merz, Κ. Μ., Jr.; Kollman, P. A. J. Fhys. Chem. 1991, 95, 6661.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1992 Springer Science+Business Media Dordrecht
About this chapter
Cite this chapter
Jorgensen, W.L., Nguyen, T.B. (1992). Structure and Binding for Cyclophane-Arene Complexes in Water From Monte Carlo Simulations. In: Balzani, V., De Cola, L. (eds) Supramolecular Chemistry. NATO ASI Series, vol 371. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-2492-8_25
Download citation
DOI: https://doi.org/10.1007/978-94-011-2492-8_25
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-5099-9
Online ISBN: 978-94-011-2492-8
eBook Packages: Springer Book Archive