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Generation, structures, relative energies, and isomerization reactions of C5H5+ cations

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Abstract

The B3LYP, MP2, and CBS-QB3 quantum chemical methods are used to study the relative energy and isomerization reactions of C5H5+ cations. Ease of generation of 14 C5H5+ isomers by ionic dissociation of halide precursors does not correlate well with carbocation stability. The reaction profiles of concerted isomerization of various C5H5+ cations to six select cations are established along with the respective transition states. The rate coefficients of these processes are estimated by using transition state theory and activation energies computed. The transition states for these six reactions are characterized with regard to position along the isomerization pathway as per Hammond’s postulate. The 6 isomerization reactions are combined to yield multi-step conversions of various C5H5+ species to the lowest energy vinylcyclopropenyl cation 1. Finally, three different routes for obtaining the select cations from C5H5Br precursors are profiled and the most favored pathways predicted.

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Data availability

All the data are derived directly from the Gaussian 09 program and are presented in this article and in the Supplementary Information.

Code availability All computations were carried out using the Gaussian 09 program, structural representations being made using the GaussView 5 program, both provided by Gaussian, Inc., USA. These are not open source programs.

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Funding

This study was funded by the Council for Scientific and Industrial Research, Government of India, through the Sanction Letter No. 34(1481)/11/EMR-II.

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Authors and Affiliations

  1. Department of Chemistry, North-Eastern Hill University, Shillong, 793 022, India

    K. S. Kharnaior, Asit K. Chandra & R. H. Duncan Lyngdoh

Authors
  1. K. S. Kharnaior
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  2. Asit K. Chandra
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  3. R. H. Duncan Lyngdoh
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Contributions

All authors contributed to the study conception and design. Literature survey, material preparation, and data collection were performed by Dr. Kiewshaphrang Kharnaior. Data analysis and interpretation were done by all the authors. The first draft of the manuscript was written by Dr. R. H. Duncan Lyngdoh and Dr. A. K. Chandra. The program URATE and its application were provided by Dr. A. K. Chandra. All authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Asit K. Chandra or R. H. Duncan Lyngdoh.

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Kharnaior, K.S., Chandra, A.K. & Lyngdoh, R.H.D. Generation, structures, relative energies, and isomerization reactions of C5H5+ cations. J Mol Model 27, 218 (2021). https://doi.org/10.1007/s00894-021-04839-5

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