The structure and dynamic behaviour of monomeric lead(ii) dithiolate Pb(SCH(2)CH(2)NMe(2))(2) are studied by multi-nuclear NMR, IR and Raman spectroscopy in solution, as well as variable-temperature Raman spectroscopy and X-ray diffraction analysis in the solid-state, revealing an unusual dynamic "flip-flop" process in solution and reversible conformational isomerism of the chelated five-membered rings in the solid-state.