Thallium(i) amides, almost unknown a decade ago, have been a recent focus of main group amide chemistry yielding a large variety of unprecedented structural motifs and patterns of reactivity. The structural chemistry in the solid state was found to be characterised by a clustering of weakly attractive metalâ metal interactions as well as metalâ arene interactions giving rise to finite or infinite aggregates. Controlled redox disproportionation of thallium(i) amides has provided access the mixed valent compounds including covalently metalâ metal bonded Tl^IIâ Tl^II complexes while stepwise metal exchange reactions have given mixed metal derivatives.