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Braga D, Chen S, Filson H, et al. 1,4-hydroxybiradical behavior revealed through crystal structure-solid-state reactivity correlations. J Am Chem Soc. 2004;126(11):3511-20doi: 10.1021/ja039076w.
Braga, D., Chen, S., Filson, H., Maini, L., Netherton, M. R., Patrick, B. O., Scheffer, J. R., Scott, C., & Xia, W. (2004). 1,4-hydroxybiradical behavior revealed through crystal structure-solid-state reactivity correlations. Journal of the American Chemical Society, 126(11), 3511-20. https://doi.org/10.1021/ja039076w
Braga, Dario, et al. "1,4-hydroxybiradical behavior revealed through crystal structure-solid-state reactivity correlations." Journal of the American Chemical Society vol. 126,11 (2004): 3511-20. doi: https://doi.org/10.1021/ja039076w
Braga D, Chen S, Filson H, Maini L, Netherton MR, Patrick BO, Scheffer JR, Scott C, Xia W. 1,4-hydroxybiradical behavior revealed through crystal structure-solid-state reactivity correlations. J Am Chem Soc. 2004 Mar 24;126(11):3511-20. doi: 10.1021/ja039076w. PMID: 15025478.
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J Am Chem Soc. 2004 Mar 24;126(11):3511-20. doi: 10.1021/ja039076w.

1,4-hydroxybiradical behavior revealed through crystal structure-solid-state reactivity correlations.

Journal of the American Chemical Society

Dario Braga, Shuang Chen, Heather Filson, Lucia Maini, Matthew R Netherton, Brian O Patrick, John R Scheffer, Carl Scott, Wujiong Xia

Affiliations

  1. Department of Chemistry, University of British Columbia, Vancouver, Canada V6T 1Z1.

PMID: 15025478 DOI: 10.1021/ja039076w

Abstract

Structure-reactivity correlations for triplet 1,4-hydroxybiradicals in solution are made difficult by the presence of multiple reactive conformers and the possibility of conformation-dependent intersystem crossing. These problems can be overcome by working in the crystalline state, where the conformations of the 1,4-hydroxybiradicals are fixed and determinable by X-ray crystallography of the parent ketones, assuming that hydrogen atom abstraction occurs with little or no change in conformation. This approach is applied to 15 bi- and tricyclic ketones designed to have slightly different biradical conformations, so that the effect of small and incremental changes in geometry on biradical behavior can be tested. The results indicate that, while geometry does have a strong influence on 1,4-hydroxybiradical partitioning between cyclization, cleavage, and reverse hydrogen transfer, a full understanding of the results requires that the strain involved in forming the cyclization products be taken into account.

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