Mercury(I) chemistry. Part I. Complexes of the mercurous ion with some arenes

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Abstract
A wide range of arene complexes of the mercurous ion has been prepared from mercurous hexafluoroarsenate and the appropriate arene in liquid sulfur dioxide. Raman spectroscopy confirmed the integrity of the dimeric Hg22+ cation in these complexes. 13C nuclear magnetic resonance spectroscopy showed that Hg22+–arene complexes exist in sulfur dioxide solution. The 13C data allowed the estimation of formation constants for the hexamethylbenzene, p-xylene, and p-dichlorobenzene complexes together with the 13C chemical shifts for the bound substrates in these cases. The 13C chemical shift changes (relative to the free substrate) on addition of Hg22+ to SO2 solutions of various methylated benzenes are compared with those occurring on complexation of the same arenes by the argentous ion and the Cr(CO)3 moiety. In mercurous ion–arene complexes, it is concluded that the cation is involved in a localized interaction with the arene and that there are preferred binding sites. These sites may be identified by the complexation shifts for the Ag+– and Hg22+–arene complexes.

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