Abstract
The tautomerism and intramolecular hydrogen shifts of 5-amino-tetrazole in the gas phase were studied in the present work. The minimum energy path (MEP) information of 5-amino-tetrazole was obtained at the CCSD(T)/6–311G**//MP2/6–311G** level of theory. The six possible tautomers of 1H, 4H-5-imino-tetrazole (a), 1H-5-amino-tetrazole (b), 2H-5-amino-tetrazole (c), 1H, 2H-5-imino-tetrazole (d), the mesoionic form (e) and 2H, 4H-5-imino-tetrazole (f) were investigated. Among these tautomers, there are 2 amino- forms, 3 imino- forms, and 1 mesoionic structure form. In all the tautomers, 2-H form (c) is the energetically preferred one in the gas phase. In the imino- tautomers, the energy value of the compound d is similar as that of the compound f but it is higher than the energy value of the compound a. The potential energetic surface (PES) and kinetics for five reactions have been investigated. Reaction 2 (b→c) was hydrogen shifts only in which the 1-H and 2-H rearrangement. This means that the reaction 2 (b→c) is energetically favorable having an activation barrier of 45.66 kcal·mol−1 and the reaction energies (ΔE) is only 2.67 kcal·mol−1. However, the reaction energy barrier for tautomerism of reaction 1 (b→e) is 54.90 kcal·mol−1. Reaction 1 (b→a), reaction 3 (c→d), and reaction 5 (c→f) were amino- →imino- tautomerism reactions. The energy barriers of amino- →imino- tautomerism reactions required are 59.39, 65.57, 73.61 kcal·mol−1 respectively in the gas phase. The calculated values of rate constants using TST, TST/Eckart, CVT, CVT/SCT and CVT/ZCT methods using the optimized geometries obtained at the MP2/6–311G** level of theory show the variational effects are small over the whole temperature range, while tunneling effects are big in the lower temperature range for all tautomerism reactions.
Similar content being viewed by others
References
Sivabalan R, Anniyappan M, Pawar SJ, Talawar MB, Gore GM, Venugopalan S et al (2006) J Hazard Mater A137:672–680 doi:10.1016/j.jhazmat.2006.03.038
Katritzky AR, Rogovoy BV, Kovalenko KV (2003) J Org Chem 68:4941–4943 doi:10.1021/jo0266543
Jime’nez V, Alderete JB (2006) J Mol Struct 775:1–7
Chen ZX, Xiao HM, Chin YN (1999) J Phys Chem A 103:8062–8066 doi:10.1021/jp9903209
Levchik SV, Ivashkevich OA, Balabanovich AI (1992) Thermochim Acta 207:115–130 doi:10.1016/0040-6031(92)80129-K
Jonassen HR, Pankert T, Henry RA (1967) Appl Spectrosc 21:89–91 doi:10.1366/000370267774385308
Nelson JH, Baglin FG (1972) Spectrosc Lett 5:101–105 doi:10.1080/00387017208064693
Murphy DB, Picard JP (1954) J Org Chem 19:1801–1817
Koz’min’ski W, Stefaniak L, Wiench JW (1995) Polish J Chem 69:74–79
Bocia W, Jaz’winsky J, Koz’minsky W, Stefaniak GA (1994) Webb J Chem Soc Perkin Trans 2:1327–1331 doi:10.1039/p29940001327
Barmin MI, Gromova SI, Kasatikova EL, Karaulova IB, V. MV (1992) Zhum Org Khim 28:1767–1771
Vander Putten N, Haeijdenrijk D, Schenk H (1974) Cryst Struct Commun :321–322
Palmer MH, Beveridge A (1987) J Chem Phys 111:249–255 doi:10.1016/0301-0104(87)80138-6
Ming WW, Regis LT, Curt W (1993) J Am Chem Soc 115:2465–2472 doi:10.1021/ja00059a048
Chen ZX, Xiao HM, Yang SL (1999) Chem Phys 250:243–248 doi:10.1016/S0301-0104(99)00336-5
Chen ZX, Xiao HM, Song WY (1999) J Mol Struct THEOCHEM 460:167–173 doi:10.1016/S0166-1280(98)00316-9
Chen ZX, Fan JF, Xiao HM (1999) J Mol Struct THEOCHEM 458:249–256 doi:10.1016/S0166-1280(98)00249-8
Chen ZX, Xiao HM (2000) Int J Quantum Chem 79:350–357 doi:10.1002/1097-461X(2000)79:6<350::AID-QUA3>3.0.CO;2-T
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR (2003) GAUSSIAN 03, Revision A.1. Gaussian, Inc, Pittsburgh, PA
Frisch MJ, Head-Gordon M, Pople JA (1990) Chem Phys Lett 166:281–289 doi:10.1016/0009-2614(90)80030-H
Head-Gordon M, Pople JA, Frisch MJ (1988) Chem Phys Lett 153:503–509 doi:10.1016/0009-2614(88)85250-3
Petersson GA, Bennett A, Tensfeldt TG, Al-Laham MA, Shirley WA, Mantzaris J (1988) J Chem Phys 89:2193–2197 doi:10.1063/1.455064
Krishnan R, Binkley JS, Seeger R, Pople JA (1980) J Chem Phys 72:650–677 doi:10.1063/1.438955
Curtiss LA, Raghavachari K, Redfern PC, Rassolv V, Pople JA (1998) J Chem Phys 109:7764–7776 doi:10.1063/1.477422
Purvis GD, Bartlett RJ (1982) J Chem Phys 76:1910–1918 doi:10.1063/1.443164
Gonzalez C, Schlegel HB (1989) J Chem Phys 90:2154–2161 doi:10.1063/1.456010
Zhang SW, Truong TN (2001) VKLab version 1.0, University of Utah
Chuang YY, Corchado JC, Fast PL, Will J, Hu WP, Liu YP et al. (1999) POLYRATE, Program vision 8.2, Minneapolis
Truhlar DG, Isaacson AD, Garrett BC (1985) Theory of Chemical Reaction Dynamics, vol. 4. CRC Press, Boca Raton
Truong NT, Truhlar DG (1990) J Chem Phys 93:1761–1769 doi:10.1063/1.459103
Miller WH (1979) J Am Chem Soc 101:6810–6814 doi:10.1021/ja00517a004
Truhlar DG, Garrett BC (1984) Annu Rev Phys Chem 35:159–189 doi:10.1146/annurev.pc.35.100184.001111
Truong NT (1994) J Chem Phys 100:8014–8025 doi:10.1063/1.466795
Liu YP, Lynch GC, Troung TN, Lu DH, Truhlar DG, Garrett BC (1993) J Am Chem Soc 115:2408–2415 doi:10.1021/ja00059a041
Truhlar DG, Isaacson AD, Garrett BC (1982) J Phys Chem 86:2252–2263 doi:10.1021/j100209a021
Harmony MD, Laurie VW, Kuczkowski RL, Schwendeman RH, Ramsay UA, Lovas FL (1979) J. Phys. Chem. Ref. 8:679–721
Zhang LP, Tu YR Trans (1980) Foundation of Organ. Chem. (Theory and Application) Beijing: the Science Press
Palmer MH, Beveridge A (1987) J Chem Phys 111:249–261 doi:10.1016/0301-0104(87)80138-6
Acknowledgments
The authors would like to thank Professor D. G. Truhlar for providing the POLYRATE 8.2 program. The project was supported by the NSAF Foundation (No. 10776002) and the 111 project (B07012) in China.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Zhang, JG., Feng, LN., Shu, YJ. et al. Theoretical studies on the tautomerism and intramolecular hydrogen shifts of 5-Amino-tetrazole in the gas phase. J Mol Model 15, 67–77 (2009). https://doi.org/10.1007/s00894-008-0374-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00894-008-0374-0