The heteroscorpionate N2S2 donor ligand bis(3,5-tertbutylpyrazol-1-yl)dithioacetate (L) was prepared as a Li+ trinuclear complex, which co-crystallizes with tetrahydrofuran (THF) solvent molecules: [Li(L)](3) center dot (2.25)THF. When [Li(L)]3 was reacted with AgBF4 or [Cu(CH3CN)(4)]BF4, the oligonuclear species [Ag(L)](3) and [Cu-5(L)(4)]BF4 were isolated and structurally characterized. The Ag+ complex presents an irregular trinuclear structure in which three AgL moieties define a central trigonal site that may potentially host a fourth metal ion. The Cu+ complex exhibits a highly symmetric pentanuclear structure in which four equivalent CuL moieties shape an internal tetrahedral site occupied by an additional Cu+ ion. According to electrospray-mass spectrometry (ESI-MS) and H-1 diffusion NMR spectroscopy, the Ag+ and Cu+ complexes maintain oligonuclear structures in solution. In particular, the Cu+ pentanuclear complex, once dissolved, rapidly equilibrates with the tetranuclear species [Cu-4(L)(3)](+). This is confirmed by the presence of two sets of NMR signals, which demonstrated a change in ratio at different complex concentrations effected by a NMR dilution titration. Variable temperature NMR experiments (210-303 K) defined the activation parameters associated with the fluxional behavior of [Cu5(L)(4)]BF4 and [Cu4(L)(3)](+), and these results are consistent with intramolecular rearrangements in both species (Delta S+ < 0).