108-07-6Relevant articles and documents
1H NMR Rate Constants and Mercury-199 FT NMR Equilibrium Constants Involved in Disulfide Cleavage by Methylmercury
Bach, Robert D.,Rajan, Sundar J.,Vardhan, Harsha B.,Lang, Timothy J.,Albrecht, Norman G.
, p. 7727 - 7734 (1981)
A 1H NMR kinetic investigation of the cleavage of dimethyl disulfide with methylmercury acetate and triethyl phosphite is described.The metal-assisted -SS- bond rupture is first order in both CH3HgII and CH3SSCH3.Mercury-199 FT NMR has been employed to measure the equilibrium constants for complexation of CH3HgOAc with CH3SSCH3 and P(OEt)3.A concomitant electrophilic and nucleophilic mechanism for -SS- bond cleavage is suggested that involves attack by P(OEt)3 on the -SS- ?* orbital of the CH3HgII complex of CH3SSCH3.
Bach,Weibel
, p. 2575,2576 (1975)
De Simone
, p. 780 (1972)
A Raman spectroscopic study of the complexation of the methylmercury(II) cation by amino acids
Alex, Serge,Savoie, Rodrigue
, p. 491 - 496 (2007/10/02)
A systematic Raman spectroscopic investigation of the complexation of CH3Hg(1+) by the standard amino acids is reported.It is shown that the vibrational bands due to the ligand-Hg and Hg-CH3 stretching modes and to the symmetric -CH3 bending mode of the -HgCH3 unit are well suited to characterize the extent of complexation and the sites of attachment of the cation.Coordination, which occurs mostly on sulfur and nitrogen atoms by substitution of a proton on the thiol group of cysteine or on amino groups in general, is best identified by the frequency of the ligand-Hg stretching vibration in the 250-550 cm-1 region of the spectrum.
Electron-Transfer Activation in Electrophilic Mechanisms. Cleavage of Alkylmetals by Mercury(II) Complexes
Fukuzumi, S.,Kochi, J. K.
, p. 7290 - 7297 (2007/10/02)
The disappearance of the transient charge-transfer (CT) absorption bands coincides with the electrophilic (SE2) cleavage of homologous series of alkyltin compounds by various mercury(II) halides, cyanide, and carboxylates.The second-order kinetics for HgCl2 cleavage afford rate constants which vary in a rather unaccountable way with the structure of the alkyltin compound and with the polarity of the solvent.Furthermore, the relative reactivities of these alkyltin compounds in the analogous electrophilic cleavage by I2 or Br2 show poor correlations with HgCl2 cleavages, in different solvents.However, the description of the activation process as an electron transfer in the precursor complex, e.g., -> +HgCl2->, stems from the CT transition energy and leads to a linear free energy relationship in which the activation free energy is equal to the driving force for the formation of the ion pair.The latter is readily dissected by eq 18 into separate changes in electronic, steric and solvation energies.With this mechanistic formulation, the reactivities of various alkyltin compounds follow a remarkably simple linear correlation with the ionization potentials and the solvent effects, in the comparison with I2 and Br2 cleavages.Moreover, the reactivities of the various mercury(II) derivatives relate directly to differences in their electron affinities.
