Light induced cis/trans isomerization of cis-[Pd(L-S,O) 2 ] and cis-[Pt(L-S,O)2 ] complexes of chelating N,N-dialkyl-N'-acylthioureas: Key to the formation and isolation of trans isomers Irradiation cis-[M(L n -S,O) 2 ] complexes (M = Pt II , Pd II ) derived from N,N-dialkyl-N'-benzoylthioureas (HL n ) with various sources of intense visible polychromatic or monochromatic light with λ < 500 nm leads to light-induced cis → trans isomerization in organic solvents. In all cases, white-light derived from several sources or monochromatic blueviolet laser 405 nm light, efficiently results in substantial amounts of the trans-isomer appearing in solution, as shown by 1 H NMR and/or reversed-phase HPLC separation in dilute solutions at room temperature. The extent and relative rates of cis/trans isomerization induced by in situ laser light (λ = 405 nm) of cis-[Pd(L 2 -S,O) 2 ] was directly monitored by 1 H NMR and 195 Pt NMR spectroscopy of selected cis-[Pt(L-S,O) 2 ] compounds in chloroform-d, both with and without light irradiation allows the δ( 195 Pt) chemical shifts cis/trans isomer pairs to be recorded. The cis/trans isomers appear to be in a photo-thermal equilibrium between the thermodynamically favored cis-isomer and its trans counterpart. In the dark the trans-isomer reverts back to the cis-complex in what is probably a thermal process. The light-induced cis/trans process is the key to preparing and isolating the rare trans-complexes which cannot be prepared by conventional synthesis as confirmed by the first example of trans-[Pd(L-S,O) 2 ]characterized by single crystal X-ray diffraction, deliberately prepared after photo-induced isomerization in acetonitrile solution.