Sodium organomercury reagents

De Smaele, T., L. Moens, R. Dams, R Sandra, J. Van de Eycken, and J. Vandyck. 1998. Sodium tetra( -propyl)borate A novel aqueous in situ derivatization reagent for the simultaneous determination of organomercury, lead- and tin-compounds with capillary gas chromatography-inductively coupled plasma mass spectrometry. J. Chromatogr. A 793 99-106. 

Sometimes the reaction conditions used in this reaction are too harsh since heating is involved and rearrangement reactions can occur. A milder method that gives better results is to treat the alkene with mercuric acetate [Hg(OAc)2] then sodium borohydride. The reaction involves electrophilic addition of the mercury reagent to form an intermediate mercuronium ion. This reacts with water to give an organomercury intermediate. Reduction with sodium... 

Ferrocene organomercurials were also used to prepare a number of other derivatives, namely, halogen-, sulfur-, or selenium-containing compounds, biferrocenyl, or triphenylmethylferrocene [Nesmeyanov, Perevalova, 0. A. Nesmeyanova 258,259)]. Lithiation or sodium metalation provided even more versatile reagents, the reactions being used by other investigators as well. 

Several efforts have been carried out to develop a new aqueous derivatization reagent. Phenylation with sodium tetraphenylborate is a promising procedure for the speciation of several metals. Its application for organomercury analysis has been comprehensively studied [10]. Sodium tetrapropylborate is another reagent that has been investigated for determining organolead, tin, and mercury compounds [1]. However, its application is limited because it is not commercially available. 

To make C-glycosides, organopalladium(II) reagents produced from the corresponding organomercurials or -stannanes are used or iodoaromatics can be employed with catalytic proportions of palladium salts. Compound 19, made by treatment of the adduct 18 with triphenylphosphine, gives 20 (R = H) in near quantitative yield on reaction with aqueous sodium bicarbonate, but when it is simply heated briefly in toluene a different elimination occurs to give the ace-toxy compound 20 (R = OAc, Scheme 7) [30]. 

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