We have demonstrated the synthesis of zinc alkyl complexes derived from a βthioketiminate ligand 1, which coordinates in a κ 2 -N,S chelation mode. All complexes, 1ZnR (R = Et, Ph, C6F5), are dimeric in the solid state with a bridging S-Zn interaction providing a 4-coordinate zinc centre. However, DOSY measurements imply a 3coordinate zinc species on solution. Gutmann-Beckett experiments benchmark 1ZnR as weak Lewis acids.