DIRECT TRANSFER OF ALIPHATIC AND AROMATIC SUBSTITUENTS FROM ORGANOSILATRANES TO MERCURY(II) SPECIES

Article abstract of DOI:10.1016/0022-328X(85)80362-4

The relative reaction rates of several silatranes (derivatives of 2,8,9-trioxa-5-aza-1-silatricyclo<3.3.3.0^1,5>undecane) and HgCl2 in acetone-d₆ to yield the corresponding organomercury compound are of the order of e.g., 5 * 10^-1 1 mol^-1 sec^-1 or slightly less, a rate that is unexpectedly high compared to the essentially inert parent organotrialkoxysilanes.Thus, the apical Si-C bond of the silatrane is extraordinarily susceptible to direct electrophilic attack by mercury(II).The rates decrease in the order CH2=CH, C6H5, p-ClC6H4 > CH3 > CH3CH2, CH3CH2CH2 > C6H11, ClCH2, Cl2CH, CH3CH2O.The effects of varying the solvent and the counterions are noted, and the probable mechanism is discussed.