Oxidation carbon-mercury bonds

Reaction Stoichiometry. The results of the stoichiometry study (see Table II) were varied but did suggest a 1 1 ozone mercurial ratio for the cleavage of a carbon-mercury bond. Several problems were evident in such a study. Since mostly only the highest oxidation states for carbon were observed in the products of partial ozonation of 1°, 2°, and 3° organomercurials, it could be assumed that ozonolysis of the C—Hg bond involved the slowest step in the total reaction sequence. Hence, some... 

This approach is especially useful for the synthesis of organopalladium and -platinum compounds. These oxidation-reduction reactions proceed via initial insertion of the transition metal into the carbon-mercury bond and subsequent loss of mercury ... 

The carbon-metal systems considered appropriate for this section (and not covered elsewhere in this series) are carbon-tin, carbon-mercury and, to a restricted extent, carbon-palladium bonds. Although or-ganomercurials and organostannanes have been studied for over a century, the former continue to attract attention because of their controlled formation by the Markovnikov oxymercuration reaction (OM) and its variants, and the latter because of newer and regiospecific methods for forming C—Sn bonds and oxidatively cleaving them. In both cases, signiticant examples of synthetically useful oxidations have... 

Addition of 19.3 g but-3-en-l-yn-l-yl methyl tellurium (0.1 mol) to a solution of 0.1 g mercury(II) oxide in 12 m/ glacial acetic acid and heating the mixture at 50-60° for 4h produced 6.8 g of 1-acetoxy-l,3-butadien-l-yl methyl tellurium. Under these conditions acetic acid adds only to the carbon-carbon triple bond d. 

Treatment of an alkene with mercuric acetate in aqueous THF results in the electrophilic addition of mercuric ion to the double bond to form an intermediate mercuri-um ion. Nucleophilic attack by H2O at the more substituted carbon yields a stable organomercury compound, which upon addition of NaBH4 undergoes reduction. Replacement of the caiton-mercury bond by a carbon-hydrogen bond during the reduction step proceeds via a radical process. The overall reaction represents Markovnikov hydration of a double bond, which contrasts with the hydroboration-oxidation process. 

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