Protolytic Cleavage of Hg–C Bonds Induced by
1‑Methyl-1,3-dihydro‑2<i>H</i>‑benzimidazole-2-selone:
Synthesis and Structural Characterization of Mercury Complexes
Joshua
H. Palmer
Gerard Parkin
10.1021/jacs.5b00840.s001
https://acs.figshare.com/articles/dataset/Protolytic_Cleavage_of_Hg_C_Bonds_Induced_by_1_Methyl_1_3_dihydro_2_i_H_i_benzimidazole_2_selone_Synthesis_and_Structural_Characterization_of_Mercury_Complexes/2178709
Multinuclear
(<sup>1</sup>H, <sup>77</sup>Se, and <sup>199</sup>Hg) NMR spectroscopy
demonstrates that 1-methyl-1,3-dihydro-2<i>H</i>-benzimidazole-2-selone,
H(sebenzim<sup>Me</sup>), a structural analogue of the selenoamino
acid, selenoneine,
binds rapidly and reversibly to the mercury centers of HgX<sub>2</sub> (X = Cl, Br, I), while X-ray diffraction studies provide evidence
for the existence of adducts of composition [H(sebenzim<sup>Me</sup>)]<sub><i>x</i></sub>HgX<sub>2</sub> (X = Cl, <i>x</i> = 2, 3, 4; X = I, <i>x</i> = 2) in the solid
state. H(sebenzim<sup>Me</sup>) 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<sup>Me</sup>)]<sub><i>x</i></sub>HgX<sub>2</sub> 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.
2015-04-08 00:00:00
selenoneine demethylates CysHgMe
mercury detoxification
77 Se
form hydrogen bonds
Protolytic Cleavage
199 Hg
mercury centers
Structural Characterization
NMR spectroscopy
protolytic cleavage
HgX 2