| Abstract
| - The synthesis of the linkage isomers of the bis(thioimidazolyl)methane family of compounds, namelyCH2(N-tim)2 (1) and CH2(S-tim)2 (2) (where tim = thio(methyl)imidazolyl) has been reinvestigatedin order to optimize the yields, to complete the characterization of these known compounds, andalso to ascertain the effect of varying heteroatom binding on their electrochemistry. During thecourse of these studies, the reactive intermediate ClCH2(S-tim) (3) was isolated and characterized.The chloromethyl derivative 3 readily decomposes on warming to give the ionic compound [CH2(μ-C4H5N2S)2CH2](Cl)2 (4), which was converted to the hexafluorophosphate salt (5) and then wascharacterized by single-crystal X-ray diffraction. It was also shown that CH2(S-tim)2 (2) could beconverted at temperatures greater than 120 °C to CH2(N-tim)2 (1) by a thermal isomerization thatproceeds via the remaining possible linkage isomer CH2(S-tim)(N-tim). Electrochemical studies on1−3 in acetonitrile reveals that each undergoes irreversible (one electron per ring) oxidations above0.7 V versus Ag/AgCl, while the ionic compound 5 shows an irreversible reduction wave centeredat −1.09 V.
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