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Protolytic Cleavage of Hg–C Bonds Induced by 1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone: Synthesis and Structural Characterization of Mercury Complexes
[Image: see text] Multinuclear ((1)H, (77)Se, and (199)Hg) NMR spectroscopy demonstrates that 1-methyl-1,3-dihydro-2H-benzimidazole-2-selone, H(sebenzim(Me)), a structural analogue of the selenoamino acid, selenoneine, binds rapidly and reversibly to the mercury centers of HgX(2) (X = Cl, Br, I), wh...
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2015
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4415037/ https://www.ncbi.nlm.nih.gov/pubmed/25822075 http://dx.doi.org/10.1021/jacs.5b00840 |
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author | Palmer, Joshua H. Parkin, Gerard |
author_facet | Palmer, Joshua H. Parkin, Gerard |
author_sort | Palmer, Joshua H. |
collection | PubMed |
description | [Image: see text] Multinuclear ((1)H, (77)Se, and (199)Hg) NMR spectroscopy demonstrates that 1-methyl-1,3-dihydro-2H-benzimidazole-2-selone, H(sebenzim(Me)), a structural analogue of the selenoamino acid, selenoneine, binds rapidly and reversibly to the mercury centers of HgX(2) (X = Cl, Br, I), while X-ray diffraction studies provide evidence for the existence of adducts of composition [H(sebenzim(Me))](x)HgX(2) (X = Cl, x = 2, 3, 4; X = I, x = 2) in the solid state. H(sebenzim(Me)) also reacts with methylmercury halides, but the reaction is accompanied by elimination of methane resulting from protolytic cleavage of the Hg–C bond, an observation that is of relevance to the report that selenoneine demethylates CysHgMe, thereby providing a mechanism for mercury detoxification. Interestingly, the structures of [H(sebenzim(Me))](x)HgX(2) exhibit a variety of different hydrogen bonding patterns resulting from the ability of the N–H groups to form hydrogen bonds with chlorine, iodine, and selenium. |
format | Online Article Text |
id | pubmed-4415037 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-44150372016-03-30 Protolytic Cleavage of Hg–C Bonds Induced by 1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone: Synthesis and Structural Characterization of Mercury Complexes Palmer, Joshua H. Parkin, Gerard J Am Chem Soc [Image: see text] Multinuclear ((1)H, (77)Se, and (199)Hg) NMR spectroscopy demonstrates that 1-methyl-1,3-dihydro-2H-benzimidazole-2-selone, H(sebenzim(Me)), a structural analogue of the selenoamino acid, selenoneine, binds rapidly and reversibly to the mercury centers of HgX(2) (X = Cl, Br, I), while X-ray diffraction studies provide evidence for the existence of adducts of composition [H(sebenzim(Me))](x)HgX(2) (X = Cl, x = 2, 3, 4; X = I, x = 2) in the solid state. H(sebenzim(Me)) also reacts with methylmercury halides, but the reaction is accompanied by elimination of methane resulting from protolytic cleavage of the Hg–C bond, an observation that is of relevance to the report that selenoneine demethylates CysHgMe, thereby providing a mechanism for mercury detoxification. Interestingly, the structures of [H(sebenzim(Me))](x)HgX(2) exhibit a variety of different hydrogen bonding patterns resulting from the ability of the N–H groups to form hydrogen bonds with chlorine, iodine, and selenium. American Chemical Society 2015-03-30 2015-04-08 /pmc/articles/PMC4415037/ /pubmed/25822075 http://dx.doi.org/10.1021/jacs.5b00840 Text en Copyright © 2015 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Palmer, Joshua H. Parkin, Gerard Protolytic Cleavage of Hg–C Bonds Induced by 1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone: Synthesis and Structural Characterization of Mercury Complexes |
title | Protolytic Cleavage of Hg–C Bonds Induced by
1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone:
Synthesis and Structural Characterization of Mercury Complexes |
title_full | Protolytic Cleavage of Hg–C Bonds Induced by
1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone:
Synthesis and Structural Characterization of Mercury Complexes |
title_fullStr | Protolytic Cleavage of Hg–C Bonds Induced by
1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone:
Synthesis and Structural Characterization of Mercury Complexes |
title_full_unstemmed | Protolytic Cleavage of Hg–C Bonds Induced by
1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone:
Synthesis and Structural Characterization of Mercury Complexes |
title_short | Protolytic Cleavage of Hg–C Bonds Induced by
1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone:
Synthesis and Structural Characterization of Mercury Complexes |
title_sort | protolytic cleavage of hg–c bonds induced by
1-methyl-1,3-dihydro-2h-benzimidazole-2-selone:
synthesis and structural characterization of mercury complexes |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4415037/ https://www.ncbi.nlm.nih.gov/pubmed/25822075 http://dx.doi.org/10.1021/jacs.5b00840 |
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