Here we describe the rhodium (I) complexes of N-phosphino-tert-butylsulfinamide ligands. This novel class of hemilabile ligands (PNSO) can work as either P,O or P,S chelating ligands when attached to the square planar rhodium center. Complexes bearing diene ligands such as [Rh(PNSO)(NBD)][TfO] and [Rh(PNSO)(COD)][TfO] provided P,O coordination, whereas [Rh(PNSO)2][TfO]-type complexes provided P,S coordination. Ligand exchange experiments with mono and bidentate phosphines afforded evidence of the hemilabile behavior of the PNSO ligands.
