Dipole moments of cobalt(III), nickel(II), palladium(II), platinum(II), copper(II) and zinc(II) complexes of five new monothio-β-diketones RC(SH) CHCOCF 3 (R = 2′-methoxyphenyl, 2′,4′-dimethoxyphenyl, 2′,5′-dimethoxyphenyl, 2′,3′,4′-trimethoxyphenyl and 2′,4′,5′-trimethoxyphenyl) were determined by static-polarization measurements. The moments clearly indicate cis-square-planar configurations for the nickel, palladium and platinum complexes. The zinc complexes have tetrahedral structures and the copper complexes perhaps have distorted cis-square-planar structure. The 1H and 19F NMR data confirm the facial configuration for the cobalt(III) complexes. The dipole moment values for the complexes vary with R: 2′,3′,4′-trimethoxyphenyl > 2′,4′-dimethoxyphenyl > 2′,4′5′-trimethoxyphenyl > 2′,5′-dimethoxyphenyl > 2′-methoxyphenyl.