The new mononuclear palladium(II) and platinum(II) [M(p-SC 6 F 4 (CF 3 )) 2 (dppe)] complexes M=Pd 1a, Pt 2a; [M(o-SC 6 H 4 (CF 3 )) 2 (dppe)] M=Pd 1d, Pt 2d as well as the previously known [M(SC 6 F 5 ) 2 (dppe)] M=Pd 1b, Pt 2b and [M(p-SC 6 HF 4 ) 2 (dppe)] M=Pd 1c, Pt 2c, have been used as metalloligands for the preparation of the heteroleptic bimetallic complexes [M 2 (μ-SRf) 2 (dppe) 2 ](SO 3 CF 3 ) 2 M=Pd, Rf=p-C 6 F 4 (CF 3 ) 3a, C 6 F 5 3b, p-C 6 HF 4 3c, o-C 6 H 4 (CF 3 ) 3d; M=Pt, Rf=p-C 6 F 4 (CF 3 ) 4a, C 6 F 5 4b, p-C 6 HF 4 4c and o-C 6 H 4 (CF 3 ) 4d. Variable temperature 19 F NMR experiments show that the fluorothiolate bridged bimetallic compounds are fluxional in solution whereas mononuclear complexes are not. The solid state X-ray diffraction structures of [Pd(p-SC 6 HF 4 ) 2 (dppe)] (1c), [Pt(SC 6 F 5 ) 2 (dppe)] (2b) and [Pt(o-SC 6 H 4 (CF 3 )) 2 (dppe)] (2d) show square-planar coordination around the metal centers. The solid state molecular structure of the compound [Pt 2 (μ-o-SC 6 H 4 (CF 3 )) 2 (dppe) 2 ](SO 3 CF 3 ) 2 (4d), exhibit a planar [Pt 2 (μ-S) 2 ] ring with the sulfur substituents in an anti configuration.