Discrete cobalt(II) and nickel(II) complexes of type ML (where L is a bis(2,4-pentanedionate) derivative incorporating a -SCH2CH2S- bridge between the gamma-carbons of respective beta-diketone units) have been synthesised and represent the first examples in which a gamma-substituted, thioether-containing beta-diketone ligand coordinates via a sulfur and oxygen donor in preference to the classical coordination mode involving both beta-diketonate oxygens.