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Computational study on the difference between the Co–C bond dissociation energy in methylcobalamin and adenosylcobalamin

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Abstract

The bond dissociation energies of the Co–C bonds in the cobalamin cofactors methylcobalamin and adenosylcobalamin were calculated using the hybrid quantum mechanics/molecular mechanics method IMOMM (integrated molecular orbital and molecular mechanics). Calculations were performed on models of differing complexities as well as on the full systems. We investigated the origin of the different experimental values for the Co–C bond dissociation energies in methylcobalamin and adenosylcobalamin, and have provided an explanation for the difficulties encountered when we attempt to reproduce this difference in quantum chemistry. Additional calculations have been performed using the Miertus–Scrocco–Tomasi method in order to estimate the influence of solvent effects on the homolytic Co–C bond cleavage. Introduction of these solvation effects is shown to be necessary for the correct reproduction of experimental trends in bond dissociation energies in solution, which consequently have no direct correlation with dissociation processes in the enzyme.

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Acknowledgements

We thank Carles Curuchet, Javier Luque and Modesto Orozco for support with the MST model and helpful discussions. Financial support from the Spanish DGES (project no. BQU2002-04110-CO2-02) and the Catalan DURSI (project no. 2001SGR00179) is acknowledged. F.M. is also grateful for the financial support of DURSI and the ICIQ foundation.

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Correspondence to Nicole Dölker.

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Dölker, N., Morreale, A. & Maseras, F. Computational study on the difference between the Co–C bond dissociation energy in methylcobalamin and adenosylcobalamin. J Biol Inorg Chem 10, 509–517 (2005). https://doi.org/10.1007/s00775-005-0662-4

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  • DOI: https://doi.org/10.1007/s00775-005-0662-4

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