The compound 2,11-dithia[3.3]orthocyclophane (L) is a mesocyclic dithioether that can act as a bidentate ligand in different conformations. In the ionic heteroleptic complexes [PtL(eta(4)-cod)][CF3SO3](2) (1), [RhL(eta(4)-cod)][CF3SO3] (2), and [IrL(eta(4)-cod)][CF3SO3] (3) (cod = 1,5-cyclooctadiene), L is coordinated in the anti I conformation both in solution and in the solid state, as revealed by an X-ray diffraction study of complex 1. However, in complexes [PdL(PPh3)(2)][SO3CF3](2) (4) and [PtL(PPh3)(2)][SO3CF3](2) (5), L exhibits two different conformations: anti I and anti II in a 40:60 ratio, as observed by H-1 and P-31 NMR spectroscopy, with no exchange up to 90 degreesC. The homoleptic complexes [PdL2][SO3CF3](2) (6) and [PtL2][SO3CF3](2) (7), with two ligands bound to the metal, display two isomers in solution, one of them with L in conformations anti I-anti II and the other with conformations anti II-anti II with a 75:25 ratio. The X-ray structure of 6 showed only the presence of the anti II-anti II isomer in the solid state. All complexes were synthesized by the reaction of a suitable chloride complex with 2 equiv of silver triflate and 1 equiv of L.